JP2006328368A - Sheet containing polylactic acid resin, method for producing the same and container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet containing a polylactic acid resin excellent in transparency and heat resistance and to provide a method for producing the sheet and to provide a container excellent in transparency and heat resistance and obtained by forming the resultant sheet. <P>SOLUTION: The sheet is composed of a resin composition obtained by formulating a polylactic acid resin with a thermoplastic resin in which deflection temperature under load measured under 1.82 MPa load is ≥75°C and the sheet has ≥0.3 mm thickness and ≤10% haze. The thermoplastic resin is preferably poly(methyl methacrylate). The method for producing the sheet containing the polylactic acid resin comprises melt-kneading the polylactic acid resin with the thermoplastic resin in which deflection temperature under load measured under 1.82 MPa load is ≥75°C, extruding the kneaded material from a die and cooling and solidifying the extruded material at 40-70°C. The container is obtained by molding the sheet and has a stretched part and unstretched part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a sheet containing a polylactic acid resin, a method for producing the same, and a container formed by molding the obtained sheet, and more specifically, a resin containing a polylactic acid resin having excellent transparency and heat resistance The present invention relates to a sheet comprising the composition, a method for producing the sheet, and a container obtained by molding the obtained sheet.

  In recent years, biodegradable polymers that are decomposed in the natural environment by the action of microorganisms existing in soil or water have attracted attention from the viewpoint of global environmental conservation, and various biodegradable polymers have been developed. Of these, as a biodegradable polymer that can be melt-molded, for example, a fat comprising an aliphatic dicarboxylic acid component such as polyhydroxybutyrate, polycaprolactone, succinic acid or adipic acid, and a glycol component such as ethylene glycol or butanediol. Family polyester and polylactic acid are well known. Among these, the polylactic acid resin can be produced at low cost by a fermentation method using microorganisms, using lactic acid as a monomer as a raw material for biomass such as corn, and has transparency and a melting point of about 170. It is expected to be a biopolymer that can be melt-molded at a high temperature. Taking advantage of such properties, it is being used as a material for various products. For example, Patent Document 1 describes that a sheet made of polylactic acid resin is used for a food container.

  However, since the polylactic acid resin has a glass transition temperature of around 60 ° C. and has a large thermal deformation and rigidity reduction near this temperature, for example, when used as a food container, it is easily deformed under normal use conditions. Therefore, there has been a demand for a polylactic acid material having excellent heat resistance that can be used as a food container.

On the other hand, a technique for blending a plurality of resins is widely known as a polymer alloy technique, and is widely used for the purpose of improving the defects of individual thermoplastic resins. For example, Patent Document 2 describes blending a polylactic acid resin and a polymethyl methacrylate resin, but does not describe any method for processing the blend into a container. Patent Document 3 describes that a film formed by blending a polylactic acid resin and a polymethyl methacrylate resin needs to use a stretched film in order to suppress deterioration in quality due to thermal deformation or the like. ing. However, in order to obtain a stretched film, a dedicated facility is required, and a material having practical heat resistance has been demanded without performing a stretching operation.
JP-A-6-298236 (page 2-4) JP-A-8-59949 (page 2-4) JP-A-2005-36054 (page 2-4)

  An object of the present invention is to provide a sheet made of a resin composition containing a polylactic acid resin having excellent transparency and heat resistance, a method for producing the sheet, and a container formed by molding the obtained sheet.

  The present invention employs the following means in order to solve such problems.

  That is, the present invention is as follows.

  (1) A polylactic acid resin having a thickness of 0.3 mm or more and a haze of 10% or less comprising a resin composition comprising a polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or higher. Including sheet.

  (2) The sheet containing the polylactic acid resin according to (1), wherein the thermoplastic resin is polymethyl methacrylate.

  (3) Weight ratio of the polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher (polylactic acid resin / a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher. (The thermoplastic resin which is) is 55 / 45-10 / 90, The sheet | seat containing the polylactic acid resin as described in (1) or (2).

  (4) The sheet | seat containing the polylactic acid resin in any one of (1)-(3) whose load deflection temperature measured by the load 1.82MPa of the said resin composition is 65 degreeC or more.

  (5) A polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or higher are melt-kneaded, extruded from a die, and cooled and solidified at 40 to 70 ° C. A method for producing a sheet containing a lactic acid resin.

  (6) The method for producing a sheet containing a polylactic acid resin according to (5), wherein melt-kneading is performed using a twin-screw extruder.

  (7) The manufacturing method of the sheet | seat containing the polylactic acid resin as described in (5) whose said thermoplastic resin is a polymethylmethacrylate.

  (8) Weight ratio of the polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher (polylactic acid resin / a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher. (Thermoplastic resin) is melt-kneaded in the range of 55/45 to 10/90, and the method for producing a sheet containing the polylactic acid resin according to any one of (5) to (7).

  (9) A sheet containing the polylactic acid resin according to any one of (1) to (4) or a sheet containing the polylactic acid resin obtained by the production method according to any one of (5) to (8). A method for producing a container having a stretched part and an unstretched part to be molded.

  (10) A sheet containing the polylactic acid resin according to any one of (1) to (4) or a sheet containing the polylactic acid resin obtained from the production method according to any one of (5) to (8) A container having a stretched part and an unstretched part.

  (11) The container according to (10), wherein the crystal melting enthalpy of the stretched portion is 5 J / g or more.

  ADVANTAGE OF THE INVENTION According to this invention, the container formed by shape | molding the sheet | seat which consists of a resin composition containing the polylactic acid resin excellent in transparency and heat resistance, its manufacturing method, and the obtained sheet | seat can be provided.

  The polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Is less than 50 mol%, and from the viewpoint of heat resistance, it is preferably 30 mol% or less, more preferably 10 mol% or less. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutyl Polycarboxylic acids such as phosphonium sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglyco Glycerin, pentaerythritol, bisphenol A, aromatic polyhydric alcohol obtained by addition reaction of bisphenol with ethylene oxide, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid, and glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ Lactones such as -butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone can be used.

  In the present invention, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component from the viewpoint of heat resistance. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90% or more. More preferably, the L-form is contained at 95% or more, or the D-form is contained at 95% or more, and the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Most preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  As a method for producing the polylactic acid resin, a known polymerization method can be used, and a direct polymerization method from lactic acid or a ring-opening polymerization method via lactide can be used.

  The molecular weight or molecular weight distribution of the polylactic acid resin is not particularly limited as long as it can be substantially molded, but the weight average molecular weight is preferably 10,000 or more, more preferably 40,000 or more, More preferably, it is 80,000 or more, and particularly preferably 100,000 or more. The upper limit is not particularly limited, but is preferably 500,000 or less, more preferably 300,000 or less, and more preferably 250,000 or less. The weight average molecular weight herein is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher.

  The thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa used in the present invention is 75 ° C. or higher, but is not particularly limited, but acrylic resins such as polymethyl methacrylate, polystyrene, acrylonitrile butadiene・ Cellulose series such as styrene (ABS) resin, acrylonitrile styrene (AS) resin, acrylonitrile styrene acrylate (ASA) resin, acrylonitrile ethylene styrene (AES) resin, methyl methacrylate styrene (MS) resin, cellulose acetate Resin, polyarylate, cyclic olefin resin, nylon 46, aromatic nylon, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyether Sulfone, polyetherimide, polyimide, polyvinyl phenol, novolak phenolic resins, and fluorine resins. In the present invention, the deflection temperature under load measured at a load of 1.82 MPa is a value measured using a 3.2 mm-thick test piece in accordance with ASTM method D648 standard.

  As a thermoplastic resin having a deflection temperature under load measured at a load of 1.82 MPa used in the present invention is 75 ° C. or more, particularly when blended with a polylactic acid resin, it has excellent heat resistance and high transparency. Acrylic resins are preferable, polymethyl methacrylate obtained by using methyl methacrylate as a vinyl monomer is more preferable, and a polymethyl methacrylate copolymer obtained by copolymerizing another vinyl monomer is more preferable. Other vinyl monomers include aromatic vinyl monomers such as α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and pt-butylstyrene. , Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic anhydride, monoethyl maleate, N-substituted maleimides such as itaconic acid, itaconic anhydride, phthalic acid, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamido N-propylmethacrylamide, acrylic acid, methyl acrylate, ethyl acrylate, aminoethyl acrylate, propylaminoethyl acrylate, methacrylic acid, cyclohexyl methacrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, Phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, butyl 2- (hydroxymethyl) acrylate, N-vinyldiethylamine, N-acetyl Vinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and And 2-styryl-oxazoline. These vinyl monomers can be used alone or in combination of two or more. In terms of heat resistance, the polymethyl methacrylate copolymer is particularly preferably a copolymer containing a cyclic structural unit such as maleic anhydride, glutaric anhydride, or maleimide ring in the main chain. More preferably, it is used in combination with methacrylate. Such a polymethylmethacrylate copolymer can be produced according to a known method. The other vinyl monomer component unit amount is preferably a copolymer obtained by copolymerization, preferably 30 mol% or less, more preferably 20 mol% or less.

  The thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa used in the present invention is 75 ° C. or more, preferably contains polymethyl methacrylate, has a weight average molecular weight of 50,000 to 450,000, a glass transition temperature of 80 It is preferable to contain at least one polymethyl methacrylate having a temperature of at least ° C and a syndiotacticity of 40% or more.

  By using polymethyl methacrylate that satisfies these conditions, the intermolecular interaction with the polylactic acid resin is increased and the affinity is improved, so the effect of improving heat resistance is increased, and transparency, heat resistance and fluidity are increased. An excellent resin composition can be obtained.

  When the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa used in the present invention is 75 ° C. or higher contains polymethyl methacrylate, the polymethyl methacrylate is excellent in heat resistance and moldability. Is preferably a weight average molecular weight of 50,000 to 450,000, more preferably 70,000 to 200,000, and even more preferably 90,000 to 150,000. The weight average molecular weight here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by GPC using hexafluoroisopropanol as a solvent.

  When the thermoplastic resin having a deflection temperature under load measured at a load of 1.82 MPa used in the present invention is 75 ° C. or higher contains polymethyl methacrylate, at least one of polymethyl methacrylate is excellent in terms of heat resistance. The glass transition temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, more preferably 100 ° C. or higher, particularly preferably 110 ° C. or higher, and most preferably 120 ° C. or higher. Although an upper limit is not specifically limited, 150 degreeC or less is preferable at the point of a moldability. The glass transition temperature here is a value measured according to the method described in JIS K7121, and is a midpoint glass transition temperature when the temperature is raised at 20 ° C./min by DSC measurement. Furthermore, in the present invention, the polymethyl methacrylate preferably contains at least one polymethyl methacrylate having a glass transition temperature of 110 ° C. or higher.

  When the thermoplastic resin having a deflection temperature under load measured at a load of 1.82 MPa used in the present invention is 75 ° C. or higher contains polymethyl methacrylate, at least one of polymethyl methacrylate is excellent in terms of heat resistance. Syndiotacticity is preferably 40% or more, more preferably 45% or more, more preferably 50% or more, particularly preferably 60% or more, and preferably 90% or less, and 80% or less in terms of fluidity. More preferred. Further, in terms of excellent heat resistance, at least one of polymethyl methacrylate is preferably heterotacticity of 45% or less, more preferably 40% or less, and even more preferably 35% or less. 30% or less is particularly preferable. In terms of excellent heat resistance, at least one polymethyl methacrylate is preferably 20% or less isotacticity, more preferably 15% or less, and even more preferably 10% or less. It is particularly preferably 5% or less. As used herein, syndiotacticity, heterotacticity, and isotacticity are 0.9 ppm, 1.0 ppm, and 1.2 ppm straight lines observed in 1H-NMR measurement using deuterated chloroform as a solvent. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, where the total integrated intensity of the peaks of the chain-branched methyl groups is 100%.

When the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa used in the present invention is 75 ° C. or higher, contains polymethyl methacrylate, two or more types of polymethyl methacrylate satisfying at least one of the following conditions are used. It is preferable that it is included.
(A) Difference in glass transition temperature is 10 ° C. or more (b) Difference in syndiotacticity is 3% or more

By using polymethyl methacrylate that satisfies these conditions, the intermolecular interaction with the polylactic acid resin is increased and the affinity is improved, so the effect of improving heat resistance is increased, and transparency, heat resistance and fluidity are increased. An excellent resin composition can be obtained.

  In the present invention, in terms of heat resistance and fluidity, the difference in glass transition temperature is preferably 15 ° C. or higher, and more preferably 20 ° C. or higher. When the difference in glass transition temperature is less than 10 ° C., the effect of improving heat resistance is insufficient. Moreover, although the upper limit of the difference of glass transition temperature is not specifically limited, It is preferable that it is 60 degrees C or less at the point of transparency. The glass transition temperature here is a value measured according to the method described in JIS K7121, and is a midpoint glass transition temperature when the temperature is raised at 20 ° C./min by DSC measurement.

  In the present invention, in terms of heat resistance and fluidity, the difference in syndiotacticity is preferably 5% or more, more preferably 7% or more, and further preferably 10% or more. If the difference in syndiotacticity is less than 3%, the heat resistance improving effect is insufficient. Moreover, the upper limit of the difference of syndiotacticity is not particularly limited, but is preferably 50% or less from the viewpoint of transparency. Syndiotacticity here means 0.9 ppm and 1.0 ppm observed as syndiotacticity, heterotacticity and isotacticity, respectively, in 1H-NMR measurement using deuterated chloroform as a solvent. The total integrated intensity of the 1.2 ppm linear branched methyl group peaks is 100%, and the ratio of the integrated intensity of each peak can be calculated as a percentage.

  In the present invention, the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher contains polymethyl methacrylate, and when two or more types of polymethyl methacrylate are used, two or more types are used. The composition of the polymethyl methacrylate is not particularly limited, but in terms of excellent heat resistance and fluidity, the polymethyl methacrylate having the highest glass transition temperature or syndiotacticity is designated as polymethyl methacrylate 1, and the glass transition The polymethyl methacrylate having the lowest temperature or syndiotacticity is defined as polymethyl methacrylate 2, and the weight ratio of polymethyl methacrylate 1 to polymethyl methacrylate 2 (polymethyl methacrylate 1 / polymethyl methacrylate 2) is 10/90 to 90 / Is preferably 0, and more preferably 60 / 40-40 / 60.

  A thermoplastic resin having a deflection temperature measured at a load of 1.82 MPa used in the present invention of 75 ° C. or higher has a glass transition temperature of + 100 ° C. and a melt flow rate (MFR) at a load of 37.2 N of 0. It is preferably 1 to 40 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, further preferably 2 to 20 g / 10 minutes, more preferably 5 to 15 g / min. 10 minutes is particularly preferred. If the MFR is less than 0.1 g / 10 minutes, the moldability tends to be lowered, and if it exceeds 40 g / 10 minutes, the heat resistance improving effect tends to be lowered.

  In the present invention, the blending ratio of the polylactic acid resin and the thermoplastic resin having a deflection temperature under load of 75 ° C. or higher measured at a load of 1.82 MPa is not particularly limited, but is a weight ratio (polylactic acid resin / load 1 Thermoplastic resin whose load deflection temperature measured at .82 MPa is 75 ° C. or higher) is preferably 99/1 to 1/99, more preferably 70/30 to 5/95, and 55/45 to 55/45. 10/90 is more preferable, and 55/45 to 30/70 is particularly preferable. By setting it as such a compounding ratio, the resin composition provided with heat resistance and transparency with sufficient balance can be obtained.

  In the present invention, it is preferable to add an impact resistance improver in terms of excellent impact resistance. The impact resistance improver used in the present invention is not particularly limited as long as it can be used for improving the impact resistance of a thermoplastic resin, but is a rubber-like substance exhibiting rubber elasticity at room temperature, for example, At least one selected from the following various impact resistance improvers can be used.

  That is, specific examples of the impact modifier include ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, various acrylic rubbers, ethylene-acrylic acid copolymer. Copolymer and alkali metal salt thereof (so-called ionomer), ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer (for example, ethylene-methyl acrylate copolymer, ethylene-acrylic acid) Ethyl copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer), ethylene-vinyl acetate copolymer, acid-modified ethylene-propylene copolymer, diene rubber (for example, polybutadiene, polyisoprene, Polychloroprene), diene and vinyl monomer Polymer (for example, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene- Styrene block copolymer, graft copolymer of styrene and polybutadiene, butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber , Silicone rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, polyester elastomer and polyamide elastomer. Further, those having various cross-linking degrees, those having various microstructures such as cis structure and trans structure, and multilayer polymers composed of a core layer and one or more shell layers covering it are also used. be able to.

  In the present invention, as the impact resistance improver, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers and graft copolymers. it can. Furthermore, when producing these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic esters and methacrylic esters. is there.

  Among these impact modifiers, a polymer containing an acrylic unit and a polymer containing a unit having an acid anhydride group and / or a glycidyl group are preferable. Preferable examples of the acrylic unit herein include methyl methacrylate units, methyl acrylate units, ethyl acrylate units and butyl acrylate units. Preferred examples of units having an acid anhydride group or glycidyl group May include maleic anhydride units and glycidyl methacrylate units.

  In the present invention, the impact resistance improver is more preferably a multilayer polymer composed of a core layer and one or more shell layers covering the core layer in terms of excellent impact resistance. It is more preferable that it is a multilayer structure polymer comprised from the polymer containing a methyl unit and / or a methyl acrylate unit. In the present invention, the multi-layer structure polymer is composed of a core layer and one or more shell layers covering the core layer, and a so-called core-shell type structure in which adjacent layers are composed of different polymers. It is a polymer having. Further, the number of layers constituting the multilayer structure polymer is not particularly limited, and may be two or more layers, and may be three or more layers or four or more layers.

  The multilayer structure polymer used in the present invention is preferably a multilayer structure polymer having at least one rubber layer therein. Here, the type of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, a rubber constituted by polymerizing a (meth) acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylenepropylene component, or the like can be given. Preferred rubbers include, for example, (meth) acrylic components such as ethyl (meth) acrylate units, butyl (meth) acrylate units, (meth) acrylic acid-2-ethylhexyl units and benzyl (meth) acrylate units, dimethyl Polymerize silicone components such as siloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, nitrile components such as acrylonitrile units and methacrylonitrile units, or conjugated diene components such as butanediene units and isoprene units. It is a rubber composed of In addition to these components, a crosslinked rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an (meth) acrylate allyl unit or a butylene glycol diacrylate unit is also preferable. Among these, from the viewpoint of transparency and impact resistance, the rubber layer is preferably a crosslinked rubber, more preferably a crosslinked rubber having a glass transition temperature of 0 ° C. or lower. , Ethyl acrylate unit, 2-ethylhexyl acrylate unit, butyl acrylate unit, benzyl acrylate unit, and allyl methacrylate unit are suitably selected and used in combination, and the allyl methacrylate unit is a rubber layer constituent unit. It is particularly preferable to use in the range of 0.005 to 3% by weight.

  In the present invention, in the multilayer structure polymer, the type of layers other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but transparency, heat resistance and resistance From the viewpoint of impact, it is preferably a polymer component having a glass transition temperature higher than that of the rubber layer. Polymers having thermoplastic properties include unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, and vinyl cyanide units. Examples include polymers containing at least one unit selected from units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units, among which unsaturated carboxylic acid alkyl ester units, unsaturated A polymer containing at least one unit selected from glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units is preferred, and at least selected from unsaturated glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units. More preferred are polymers containing one or more units.

  The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferably used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic N-hexyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, ( Chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6 (meth) acrylic acid -Pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, amino acid acrylate Examples include ethyl, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, and the like in terms of having a large effect of improving impact resistance. Methyl methacrylate is preferably used. These units can be used alone or in combination of two or more.

  The glycidyl group-containing vinyl-based unit is not particularly limited, and examples thereof include glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene. And glycidyl (meth) acrylate is preferably used in that the effect of improving impact resistance is great. These units can be used alone or in combination of two or more.

  Examples of the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, and the maleic anhydride is effective in improving impact resistance. Acid is preferably used. These units can be used alone or in combination of two or more.

  The aliphatic vinyl unit may be ethylene, propylene or butadiene, and the aromatic vinyl unit may be styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexyl. Styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, halogenated styrene, etc., as vinyl cyanide units, maleimides such as acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. Units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide and other unsaturated dicarboxylic acid units such as maleic acid, maleic acid monoethyl ester, itaconic acid and phthalic acid, and other vinyl units such as acrylamide, methacrylamide, N-methylacrylamide, Butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 -Acroyl-oxazoline or 2-styryl-oxazoline can be mentioned, and these units can be used alone or in combination of two or more.

  As the multilayer structure polymer used in the present invention, the type of the shell layer is not particularly limited, and is an unsaturated carboxylic acid alkyl ester unit, a glycidyl group-containing vinyl unit, an aliphatic vinyl unit, an aromatic Examples thereof include polymers containing vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units and / or other vinyl units. From the viewpoint of impact, a multilayer structure polymer composed of a polymer containing methyl methacrylate units and / or methyl acrylate units is preferred.

  As a multilayer structure polymer used by this invention, a commercial item may be used as what satisfy | fills the conditions mentioned above, and it can also produce by a well-known method.

  Examples of commercially available products include "Metablen" manufactured by Mitsubishi Rayon, "Kane Ace" manufactured by Kaneka, "Paraloid" manufactured by Rohm and Haas, "Staffroid" manufactured by Gantz Kasei, or "Paraface" manufactured by Kuraray. A single compound or two or more compounds can be used.

  As a known method, an emulsion polymerization method is more preferable. As a production method, a desired monomer mixture is first emulsion-polymerized to form core particles, and then another monomer mixture is emulsion-polymerized in the presence of the core particles to form a shell layer around the core particles. Make core-shell particles to form. Further, in the presence of the particles, another monomer mixture is emulsion-polymerized to form core-shell particles that form another shell layer. Such a reaction is repeated to obtain a multilayer polymer composed of a desired core layer and one or more shell layers covering it. The polymerization temperature for forming the (co) polymer of each layer is preferably 0 to 120 ° C., more preferably 5 to 90 ° C. for each layer.

  The emulsifier used in the emulsion polymerization is not particularly limited, but is selected depending on the polymerization stability and a desired average primary particle size, and a known emulsifier such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant is used alone or It is preferable to use 2 or more types, and an anionic surfactant is more preferable. Anionic surfactants include, for example, carboxylic acid salts such as sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, sulfonates such as sodium dioctyl sulfosuccinate and sodium dodecylbenzene sulfonate, and sodium lauryl sulfate. Examples thereof include sulfate ester salts and phosphate ester salts such as sodium mono-n-butylphenylpentaoxyethylene phosphate. The addition amount of the emulsifier is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the total amount of monomers used.

  The polymerization initiator used for emulsion polymerization is not particularly limited, but includes inorganic peroxides such as potassium persulfate and ammonium persulfate, hydrogen peroxide-ferrous salt, potassium persulfate-acidic sodium sulfite, Start of water-soluble redox initiators such as ammonium sulfate-acidic sodium sulfite, water-soluble redox systems such as cumene hydroperoxide-sodium formaldehyde sulfoxylate, tert-butyl hydroperoxide-sodium formaldehyde sulfoxylate Among them, inorganic peroxide initiators and water-oil-soluble redox initiators are preferable. The addition amount of the polymerization initiator is preferably 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of the monomers used.

The multilayer structure polymer used in the present invention preferably satisfies at least one of the following conditions in terms of transparency and impact resistance.
(C) Refractive index is 1.45 to 1.50
(D) including a constituent having a glass transition temperature of 30 ° C. or lower

  Furthermore, the refractive index of the multilayer structure polymer is more preferably 1.465 to 1.495 in terms of excellent transparency. Further, the difference between the refractive index of the matrix resin phase composed of a polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or more and the refractive index of the multilayer structure polymer is 0.05. Or less, more preferably 0.02, and even more preferably 0.01 or less. In the present invention, the refractive index is a value measured at 23 ° C. and a wavelength of 589 nm using an Abbe refractometer. Further, when the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher is polymethyl methacrylate, the refractive index of the resin phase composed of polylactic acid resin and polymethyl methacrylate is polylactic acid. When the blending amount of polymethyl methacrylate in 100 parts by weight of the total of the resin and polymethyl methacrylate is x parts by weight, it can be expressed as 0.03 × x / 100 + 1.46.

  Furthermore, the multilayer structure polymer used in the present invention is more preferably a component having a glass transition temperature of 0 ° C. or lower and a component having a temperature of −30 ° C. or lower in terms of impact resistance. Is more preferable, and it is particularly preferable that it contains a constituent component of −40 ° C. or lower. In the present invention, the glass transition temperature is a value measured using a differential scanning calorimeter at a rate of temperature increase of 20 ° C./min.

  In the present invention, the average primary particle diameter of the multilayer structure polymer is not particularly limited, but is preferably 10 to 10,000 nm, more preferably 20 to 1,000 nm in terms of transparency and impact resistance. It is more preferable that it is 50-700 nm, and it is most preferable that it is 100-500 nm. In the present invention, the average primary particle diameter is the number average primary particle diameter obtained by observing an average of 20,000 times using an electron microscope, measuring the primary particle diameter of 100 arbitrary particles, and specifically, Can be determined by observing the dispersion form of the multilayer structure polymer in the resin composition with an electron microscope.

  In the present invention, the blending amount of the impact resistance improver is not particularly limited, but in terms of impact resistance, the deflection temperature under load measured with a polylactic acid resin and a load of 1.82 MPa is 75 ° C. or more. 0.1 to 200 parts by weight is preferable, 1 to 100 parts by weight is more preferable, 5 to 50 parts by weight is further preferable, and 10 to 30 parts by weight is particularly preferable with respect to a total of 100 parts by weight of a certain thermoplastic resin.

  In the present invention, in terms of transparency, heat resistance and impact resistance, the dispersed particle size of the impact resistance improver in the resin composition is preferably 1 to 1000 nm, and preferably 50 to 750 nm. More preferably, it is more preferable that it is 100-500 nm. In the present invention, the dispersed particle diameter means the number average dispersed particle diameter obtained by observing the resin composition at 20,000 times using an electron microscope, measuring the dispersed particle diameter for 100 arbitrary dispersed particles, and averaging them. It is. The dispersed particles are a total value of the number of aggregated particles (l) obtained by the following criteria and the number of non-aggregated particles (m).

  In the present invention, in terms of transparency, heat resistance, and impact resistance, the ratio (l) of the number of aggregated particles (l) and the number of unaggregated particles (m) of the impact modifier in the resin composition (l) / M) is preferably 0 to 0.5, and more preferably 0 to 0.4. In the present invention, the number of agglomerated particles and the number of non-aggregated particles were observed by 20,000 times the resin composition using an electron microscope. Were in contact with each other. Further, l indicates the total number of dispersed particles involved in aggregation, that is, when three dispersed particles are aggregated to form one aggregate, it is calculated as l = 3.

  In the present invention, the reactive compound can be selected from a glycidyl group, an acid anhydride group, a carbodiimide group, and an oxazoline group in that the transparency, heat resistance and impact resistance can be improved, and hydrolysis resistance can be improved. It is preferable to incorporate a reactive compound containing at least one functional group. In the present invention, when a multilayer structure polymer is blended, it is preferable to blend a reactive compound because the dispersibility of the multilayer structure polymer is improved and the impact resistance improving effect is increased.

  In the present invention, as the reactive compound containing a glycidyl group, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, and an alicyclic epoxy compound can be preferably used. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as sidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone; Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

  Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisamino Examples include methylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

  Examples of glycidylimide compounds include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6- Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N -Glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethyl Succinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, etc. be able to. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4, 5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like. In addition, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol nozolac type epoxy resins, and the like can be used.

  In the present invention, examples of the reactive compound containing an acid anhydride group include succinic anhydride, maleic anhydride, and phthalic anhydride. Furthermore, the polymer etc. which contain an above-described compound as a monomer unit can be mentioned.

  In the present invention, the reactive compound containing a carbodiimide group is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule, for example, in the presence of a suitable catalyst. The organic isocyanate can be heated and produced by a decarboxylation reaction.

  Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene- Su-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N , N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N ′ -Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrof Phenylcarbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-tolylcarbodiimide N, N′-benzylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, N-benzyl-N′-phenylcarbodiimide, N-octadecyl-N′-tolylcarbodiimide, N-cyclohexyl-N′-tolylcarbodiimide, N -Phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'- Di-o-isopropylphenylcarbodiimide, N, '-Di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide N, N′-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N′-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N′-di-2,4,6-trimethylphenyl Mono- or dicarbodiimide compounds such as carbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6 -Hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodi) Imide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′- Diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly ( And polycarbodiimides such as triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide). Of these, N, N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide and polycarbodiimide are preferred.

  In the present invention, examples of the reactive compound containing an oxazoline group include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2 -Pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2-decyloxy-2-oxazoline 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2-phenoxy-2 -Oxazoline, 2-Credit 2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m-ethylphenoxy-2-oxazoline, 2 -M-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2 -Oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2- Xazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2-o-propyl Phenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl-2-oxazoline, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4′-dimethyl-2-oxazoline), 2,2 '-Bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl Ropyl-2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline), 2,2′-bis (4-phenyl-) 2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline) ), 2,2′-m-phenylenebis (2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazoline) 2,2′-p-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-m-phenylene Screw (4,4'- Methyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2, 2'-octamethylenebis (2-oxazoline), 2,2'-decamethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylene Bis (4,4′-dimethyl-2-oxazoline), 2,2′-9,9′-diphenoxyethanebis (2-oxazoline), 2,2′-cyclohexylenebis (2-oxazoline), 2, And 2'-diphenylenebis (2-oxazoline). Furthermore, the polyoxazoline compound etc. which contain the above-mentioned compound as a monomer unit can be mentioned.

  In the present invention, the reactive compound is preferably a polymer having a weight average molecular weight of 1,000 to 300,000, and more preferably 5,000 to 250,000, in that bleed out can be suppressed. Here, the weight average molecular weight is a PMMA equivalent weight average molecular weight measured by GPC using hexafluoroisopropanol as a solvent. Such a reactive compound is a polymer in which at least one functional group selected from a glycidyl group, an acid anhydride group, a carbodiimide group, and an oxazoline group is introduced into the main chain or side chain in the molecule. Preferably, the polymer may be either a homopolymer or a copolymer, and any of a random copolymer, a block copolymer, a graft copolymer, and the like can be used as the copolymer.

  In the present invention, the reactive compound is preferably a polymer containing a glycidyl group-containing vinyl-based unit in terms of transparency, heat resistance and impact resistance.

  In the present invention, specific examples of the raw material monomer for forming the glycidyl group-containing vinyl unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate, maleic acid, itaconic acid And unsaturated glycidyl ethers such as monoglycidyl ester or polyglycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-4-glycidyl ether, and the like. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit preferably contains a vinyl-based unit other than the glycidyl group-containing vinyl-based unit as a copolymerization component. Depending on the selection, the melting point of the polymer, the glass transition temperature, etc. Can be adjusted. Examples of vinyl units other than glycidyl group-containing vinyl units include acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic anhydride units, unsaturated dicarboxylic acid units, and aliphatic types. Examples thereof include vinyl units, maleimide units, and other vinyl units.

  Specific examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , Isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Roxypropyl, hydroxypropyl methacrylate, acrylic acid ester or methacrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, Acrylic vinyl units having an amino group such as acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. The raw material monomer etc. which form are mentioned, Especially, acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid Methyl, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Preferred are 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile, and acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylo Tolyl, methacrylonitrile is used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer that forms the vinyl carboxylate unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Monofunctional aliphatic vinyl carboxylates such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate and vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl cinnamate, etc. And polyfunctional vinyl carboxylates such as vinyl aromatic carboxylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonic acid and vinyl sorbate. Among them, vinyl acetate is preferably used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer for forming the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, 4 -Dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned, among which styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  Examples of the raw material monomer that forms the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, among which maleic anhydride is preferably used. . These may be used alone or in combination of two or more.

  Examples of the raw material monomer for forming the unsaturated dicarboxylic acid-based unit include maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid and the like. Among these, maleic acid and itaconic acid are preferably used. These may be used alone or in combination of two or more.

  Examples of raw material monomers for forming aliphatic vinyl units include ethylene, propylene, and butadiene. Examples of raw material monomers for forming maleimide units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- As other raw material monomers for forming vinyl units such as isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide or N- (chlorophenyl) maleimide, N-vinyldiethylamine, N- Acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene and the like can be mentioned, and these can be used alone or in combination of two or more.

  In the present invention, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited, but is preferably in the range of 30 to 100 ° C. in terms of excellent handling properties. More preferably, it is in the range of ˜70 ° C., most preferably in the range of 50 to 65 ° C. The glass transition temperature here is an intermediate point glass transition temperature measured by DSC at a rate of temperature increase of 20 ° C./min by the method of JIS K7121. In addition, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit can be controlled by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit usually contains a volatile component because unreacted raw material monomers and solvents remain. The amount of the non-volatile component that is the balance is not particularly limited, but it is preferable that the non-volatile component amount is large from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by weight or more, more preferably 97% by weight or more, even more preferably 98% by weight or more, and most preferably 98.5% by weight or more. preferable. In addition, the non-volatile component here represents the residual ratio when 10 g of a sample is heated at 110 ° C. for 1 hour in a nitrogen atmosphere.

  In the present invention, a polymer containing a glycidyl group-containing vinyl-based unit may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. Contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing an unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, the method for producing a polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. When these methods are used, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used, but these remain as impurities in a polymer containing a vinyl unit containing a glycidyl group finally obtained. There are things to do. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, particularly 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  As a method for producing a polymer containing a glycidyl group-containing vinyl-based unit that satisfies the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, and the like as described above, the polymer is heated at a high temperature of 150 ° C. or higher. A method of continuous bulk polymerization under a pressure condition (preferably 1 MPa or more) in a short time (preferably 5 to 30 minutes) has a high polymerization rate, a polymerization initiator or a chain transfer agent that causes impurities and sulfur content And more preferable in that no solvent is used.

  In this invention, the compounding quantity of a reactive compound is 0.01-30 weight with respect to a total of 100 weight part of polylactic acid-type resin and the thermoplastic resin whose load deflection temperature measured by the load 1.82MPa is 75 degreeC or more. Part is preferable, 0.05 to 20 parts by weight is more preferable, 0.1 to 10 parts by weight is further preferable, and 0.5 to 3 parts by weight is particularly preferable. If the compounding amount of the reactive compound is less than 0.01 parts by weight, the impact resistance improving effect of the resin composition tends to be insufficient, and if it exceeds 30 parts by weight, the fluidity is reduced due to gelation or the like. There is a risk of lowering.

  In the present invention, it is preferable to further mix inorganic particles from the viewpoint of heat resistance, the short axis length of the inorganic particles in the resin composition is 1 to 300 nm, and the long axis length is 1 to 1000 nm. Preferably there is. In terms of transparency, the short axis length of the inorganic particles is more preferably 5 to 200 nm, further preferably 10 to 100 nm, and the long axis length is 10 to 900 nm. More preferably, it is 50-800 nm. In the present invention, the short axis length and the long axis length of the inorganic particles are obtained by observing the resin composition at 20,000 times using an electron microscope, and about 20 arbitrary inorganic particles, preferably 100 The shape is observed and measured, and the shortest length is taken as the minor axis direction, the longest length is taken as the major axis direction, and each is an average value.

  In the present invention, the inorganic particles may be granular, spherical, plate-like, or fibrous, but are preferably plate-like from the viewpoint of heat resistance.

  In the present invention, the granular or spherical inorganic particles include zinc oxide, magnesium oxide, iron oxide, titanium oxide, titania, zirconia, ceria, alumina, silica, calcium carbonate, talc, mica, kaolin, graphite powder, carbon black and the like. Among them, silica is preferable.

  In the present invention, as the plate-like inorganic particles, silicates such as talc, mica, glass flakes, montmorillonite and smectite can be used, and among them, silicates are preferable.

  In the present invention, glass fiber, carbon fiber, zinc oxide, alumina, calcium titanate, potassium titanate, barium titanate, aluminum borate, magnesium borate, magnesium oxysulfate fiber, etc. are used as the fibrous inorganic particles. be able to.

  In the present invention, the inorganic particles are more preferably those containing silicon, and specific examples include silica and silicate. Among them, layered silicate is more preferable, and organically modified layered silicate is preferable. More preferably. In the present invention, by performing elemental analysis using an electron microscope-energy dispersive X-ray analyzer (EDX), it can be determined that the particles are inorganic particles, and silicon can be detected. .

  In the present invention, the silica may be powder, water or an organic solvent dispersion type sol (colloidal silica), but colloidal silica is preferable in terms of transparency. Furthermore, in terms of transparency, the surface is treated with at least one functional group selected from a hydroxyl group, amino group, amide group, carboxyl group, glycidyl group, acid anhydride group, carbodiimide group, and oxazoline group. Is preferred. By using the surface-treated silica, the affinity with the matrix resin is improved, which is effective in suppressing aggregation and dispersibility of the inorganic particles, and can be uniformly dispersed in the resin composition. A resin composition having excellent transparency can be obtained.

  In the present invention, the organically modified layered silicate is a layered silicate in which an exchangeable cation or anion existing between layers is exchanged with an organic onium ion or an organic anion, and in particular, the exchangeable cation is an organic onium ion. Exchanged layered silicates are preferred.

  A layered silicate having exchangeable ions between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 Å are laminated, and exchangeable ions are provided between the layers of the plate-like materials. have. The ion exchange capacity is 0.2 to 3 meq / g, and preferably the ion exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li type Fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, swellable mica such as Li-type tetrasilicon fluorine mica, hydrotalcite, etc. good. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.

  Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  As quaternary ammonium ions, benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecylammonium Alkyltrimethylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldialkylammonium ions such as dimethyldioctadecylammonium, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, benzene Such as benzethonium ion having two thereof.

  In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group.

  Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more.

  Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  Examples of the organic anion include a long-chain carboxylic acid, and examples thereof include lauric acid, decanoic acid, stearic acid, dodecadicarboxylic acid, and dimer acid.

  In the present invention, the organically modified layered silicate can be produced by reacting a layered silicate having an exchangeable cation or anion between layers, an organic onium ion or an organic anion by a known method. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a liquid or molten organic salt with a layered silicate can be used.

  In the present invention, the amount of organic ions relative to the layered silicate is the cation exchange capacity of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. In general, it is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents.

  In addition, it is preferable to use the organically modified layered silicate after pretreatment with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the organically modified layered silicate is preferably uniformly dispersed in the resin composition. Uniform dispersion here means that the layered silicate is dispersed in a laminated state of 5 layers or less without having a local mass.

  In this invention, the compounding quantity of an inorganic particle is 0.1-50 weight with respect to a total of 100 weight part of a polylactic acid-type resin and the thermoplastic resin whose load deflection temperature measured by load 1.82MPa is 75 degreeC or more. Part is preferable, 0.5 to 20 parts by weight is more preferable, and 1 to 10 parts by weight is particularly preferable.

  To the resin composition used in the present invention, fillers (glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers, glass flakes, glass beads, ceramic fibers, ceramics, and the like are not impaired. Beads, asbestos, wollastonite, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, Including aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite and clay, stabilizers (antioxidants, UV absorbers, etc.), lubricants, mold release agents, flame retardants, dyes and pigments Add colorants, nucleating agents, antistatic agents, etc. Door can be. Especially, it is preferable to mix | blend a lubricant from the point that the resin composition excellent in a moldability, heat resistance, transparency, etc. is obtained. As the lubricant, those usually used for thermoplastic resin lubricants can be used. Specifically, fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, partially aliphatic saponified esters, paraffin, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohols Examples include esters, fatty acid polyglycol esters, and modified silicones. Among them, fatty acid metal salts such as calcium stearate, magnesium stearate, and calcium montanate, fatty acid amides such as stearic acid amide and erucic acid amide, ethylenebisstearic acid Alkylene bis fatty acid amides such as amides and ethylene bislauric acid amides are preferred. The blending amount of the lubricant is preferably 0.01 to 3 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin and the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or more. More preferred is 03-2 parts by weight.

  In addition, other thermoplastic resins (for example, polyethylene, nylon 6, polybutylene terephthalate, polybutylene succinate, polybutylene adipate, etc.) can be used as long as the object of the present invention is not impaired with respect to the resin composition used in the present invention. And thermosetting resins (eg phenolic resin, melamine resin, polyester resin, silicone resin, epoxy resin, etc.) and soft thermoplastic resins (eg ethylene / glycidyl methacrylate copolymer, polyester elastomer, polyamide elastomer, ethylene / propylene terpolymer, Ethylene / butene-1 copolymer, etc.) can be further blended.

  The production method of the resin composition used in the present invention is not particularly limited. For example, a polylactic acid resin, a thermoplastic resin having a deflection temperature measured at a load of 1.82 MPa and a load deflection temperature of 75 ° C. or higher, and as necessary Depending on the pre-blending of other additives, a method of uniformly melting and kneading with a single or twin screw extruder above the melting point, a method of removing the solvent after mixing in the solution, etc. are used. In terms of transparency, a method of uniformly melt-kneading with a single-screw or twin-screw extruder is preferable, and in terms of transparency, a method of uniformly melt-kneading with a twin-screw extruder is more preferable.

  In the present invention, the deflection temperature under load measured at 1.82 MPa of the resin composition forming the sheet is preferably 65 ° C or higher, more preferably 70 ° C or higher, and further 75 ° C or higher. It is preferably 80 ° C. or higher. Here, the deflection temperature under load is a value measured with a test piece having a thickness of 3.2 mm in accordance with the ASTM method D648 standard.

  The melt flow rate (MFR) of the resin composition used in the present invention is not particularly limited, but the MFR measured at 210 ° C. and 21.2 N load according to JIS K7210 is preferably 0.1 to 40 g / 10 min. 1 to 20 g / 10 min is more preferable, and 1 to 5 g / 10 min is further preferable. If the MFR is 0.1 g / 10 min or less, the load on the melt-kneading apparatus tends to increase, and a stable resin composition tends to be difficult to obtain. If it exceeds 40 g / 10 min, the heat resistance tends to decrease. .

  The sheet of the present invention has a thickness of 0.3 mm or more. From the viewpoint of heat resistance, it is preferably 0.31 mm or more, more preferably 0.4 mm or more, further preferably 0.7 mm or more, and particularly preferably 0.9 mm or more. When the thickness is less than 0.3 mm, it tends to be difficult to obtain a container having heat resistance when the container is formed using a sheet, which is not preferable. The upper limit is not particularly limited, but is preferably 10 mm or less, more preferably 3 mm or less, and even more preferably 1.5 mm or less from the viewpoint of transparency and processability when making into a container.

  The sheet of the present invention has a haze of 10% or less. Here, haze is a value obtained by measuring a sheet of the present invention having a thickness of 0.3 mm or more according to JIS K7105. The lower limit of the thickness is preferably 0.31 mm or more, more preferably 0.4 mm or more, still more preferably 0.7 mm or more, and particularly preferably 0.9 mm or more. Is preferably 10 mm or less, more preferably 3 mm or less, and even more preferably 1.5 mm or less. In terms of transparency, the haze is preferably 5% or less, and more preferably 3% or less. Although a minimum is not specifically limited, If it is 0.1% or more, it can be used practically without a problem.

  The surface hardness (pencil hardness) of the sheet of the present invention is not particularly limited, but the pencil hardness measured according to JIS K5600-5-4 is not less than HB in that the container formed from this sheet is hardly damaged. It is preferable that it is H or more. The upper limit is not particularly limited, but is preferably 3H or less, and more preferably 2H or less, in that the food container is less likely to be destroyed by impact such as dropping. A sheet having such surface hardness (pencil hardness) can be obtained, for example, by using the preferred thermoplastic resin.

  In the sheet of the present invention, when the thermoplastic resin whose load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher is polymethyl methacrylate, the syndiotacticity of isolating polymethyl methacrylate in the resin composition The tacticity ratio (syndiotacticity / isotacticity) is preferably 2.5 to 8.0. Further, from the viewpoint of heat resistance and fluidity, it is more preferably 3.0 to 8.0, further preferably 3.0 to 5.5, and 3.0 to 5.0. Particularly preferred. Syndiotacticity, heterotacticity, and isotacticity mentioned here are observed as syndiotacticity, heterotacticity, and isotacticity, respectively, in 1H-NMR measurement using deuterated chloroform as a solvent. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, with the total integrated intensity of the peaks of straight chain branched methyl groups of 0.9 ppm, 1.0 ppm, and 1.2 ppm being 100%. .

  In the sheet of the present invention, when the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher is polymethyl methacrylate, the glass transition temperature can be observed as a single one. In terms of heat resistance, the temperature range is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, further preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher. . Although an upper limit is not specifically limited, It is preferable that it is 150 degrees C or less at a fluid point, and it is more preferable that it is 120 degrees C or less. The glass transition temperature here is a value measured by DSC according to the method described in JIS K7121, and may be either the midpoint glass transition temperature or the extrapolation transition end temperature. In the DSC measurement, the DSC curve is bent by the change in specific heat capacity, and the glass transition temperature region can be detected by the shape in which the base line moves in parallel. The midpoint glass transition temperature refers to the tangent lines of the respective base lines below the bending point and above the bending point so as to be parallel to each other, and at each position where the specific heat capacity change is halved. This is the intersection of a DSC curve that draws a straight line parallel to the baseline and bends. The extrapolation transition end temperature refers to the intersection of the tangent line of the base line of the temperature above the bending point and the tangent line of the point having the maximum inclination at the bent part.

  In the method for producing a sheet of the present invention, a polylactic acid resin and a thermoplastic resin having a deflection temperature measured at a load of 1.82 MPa are melt-kneaded and then extruded from a die and cooled and solidified at 40 to 70 ° C. It is characterized by that. If the temperature for cooling and solidifying is less than 40 ° C, the sheet tends to be torn easily, and it is difficult to obtain a sheet having excellent surface smoothness. If it is 70 ° C or more, unevenness in thickness tends to occur. It tends to be difficult to obtain a sheet having excellent smoothness, which is not preferable. Moreover, 50-65 degreeC is preferable and, as for the temperature which solidifies by cooling in terms of surface smoothness, 55-65 degreeC is more preferable.

  A method for melt kneading a polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher is not particularly limited, but is a polylactic acid resin, a load deflection temperature measured at a load of 1.82 MPa. A method of blending a thermoplastic resin having a temperature of 75 ° C. or higher and other additives as necessary, and then uniformly melting and kneading with a single or twin screw extruder at a melting point or higher, a solvent after mixing in a solution However, a method of uniformly melting and kneading with a single screw or twin screw extruder is preferable from the viewpoint of productivity, and a method of uniformly melting and kneading with a twin screw extruder is preferable from the viewpoint of transparency. More preferred.

  The temperature for melt kneading is not particularly limited, but the lower limit is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, further preferably 250 ° C. or higher, and the upper limit is preferably 350 ° C. or lower, more preferably 300 ° C. or lower. preferable. If it is less than 150 ° C., the transparency tends to decrease, and if it exceeds 350 ° C., the heat resistance tends to decrease, such being undesirable.

  In the present invention, the method of extruding from a die after melt-kneading a polylactic acid resin and a thermoplastic resin having a deflection temperature under load of 752 ° C. measured at a load of 1.82 MPa is not particularly limited. The melted and kneaded product may be cooled and solidified to form a pellet and then melted again, and the melt may be extruded from the die. In the present invention, any die may be used as long as it can be shaped into a sheet shape such as a T-die.

  Any method may be used as the method for cooling the melt extruded from the die as long as it can be cooled and solidified at 40 to 70 ° C. For example, the surface temperature is 40 to 70 ° C, preferably 50. By sandwiching between two rolls (first roll and second roll) whose temperature is controlled to be ˜65 ° C., a sheet having excellent surface smoothness and less uneven thickness can be obtained. Furthermore, it is preferable that the sheet-like material narrowly supported by the first roll and the second roll is peeled off after being temporarily adhered to the second roll and conveyed to the third roll, thereby reducing the warpage of the sheet. More preferably, the sheet-like material is brought into contact with a third roll whose temperature is controlled so that the surface temperature is 20 to 80 ° C, preferably 30 to 60 ° C.

  In the present invention, the take-up speed of the cooled and solidified sheet-like material is preferably as fast as possible from the viewpoint of sheet productivity, but is preferably below the extrusion speed in terms of transparency and heat resistance. Here, the take-off speed refers to the length of the sheet-like material per unit time in the take-up direction until the sheet-like material peels from the second roll and comes into contact with the third roll, and the extrusion speed is It means the length of the sheet-like material per unit time in the take-out direction extruded from the die.

  The container of the present invention is a container having a stretched part and an unstretched part, which is obtained by molding the sheet of the present invention or a sheet obtained from the sheet manufacturing method.

  In the present invention, the determination of the stretched portion and the unstretched portion can be obtained from [the thickness of each part of the container / the thickness of the sheet] by measuring the thickness of each part of the container with respect to the thickness of the sheet to be used. If the [thickness of each part of the container / the thickness of the sheet] is less than 1, it is the stretched part, and if it is 1 or more, it is the unstretched part.

  In the container of the present invention, in terms of heat resistance, the crystal melting enthalpy of the stretched portion is preferably 5 J / g or more, more preferably 10 J / g or more, and further preferably 15 J / g or more. 20 J / g or more is particularly preferable. Although an upper limit is not specifically limited, Usually, it is about 40 J / g. If the crystal melting enthalpy of the stretched portion is less than 5 J / g, the heat resistance tends to decrease, such being undesirable. In the present invention, a method for obtaining a container having a preferable crystal melting enthalpy of the stretched part is not particularly limited, but it is preferable to heat treat the sheet or the container. As the heat treatment conditions, the temperature is preferably 80 to 160 ° C, more preferably 90 to 140 ° C, and the treatment time is preferably 0.1 to 60 seconds, more preferably 1 to 30 seconds. In the present invention, the crystal melting enthalpy of the stretched portion is a value measured using a differential scanning calorimeter (DSC) under a temperature increase rate of 20 ° C./min.

  In the present invention, the method for molding the container is not particularly limited, but vacuum molding and press molding are preferable in terms of productivity.

  A general-purpose molding machine can be used as the vacuum molding. For example, the sheet is heated at a temperature of 60 to 150 ° C., preferably 65 to 120 ° C., more preferably 70 to 90 ° C. using a heater such as a hot plate or hot air, and the mold temperature is 30 to 150 ° C., The container can be obtained by molding by reducing the pressure in the mold at the same time that the mold is set to preferably 40 to 100 ° C., more preferably 50 to 90 ° C.

  As press molding, a general-purpose molding machine can be used. For example, the sheet is heated at a temperature of 60 to 150 ° C., preferably 65 to 120 ° C., more preferably 70 to 90 ° C. using a heater such as a hot plate or hot air, and the mold temperature is 30 to 150 ° C., The container can be obtained by molding by pressing and clamping using a male mold and a female mold set to 40 to 100 ° C., more preferably 50 to 90 ° C.

  The container of the present invention includes containers for trays, plates and cups and food applications such as lids and covers used in connection with them, as well as blister pack containers, daily goods, sanitary goods, household goods, agriculture, horticulture, etc. It can be used as a container useful in various fields.

Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. Here, the compounding ratio in an Example shows weight%. Moreover, the raw material used and the code | symbol in a table | surface are shown below.
(A) Polylactic acid resin (A-1) Poly L lactic acid resin (D-form 1.2%, weight average molecular weight (PMMA conversion) 210,000)
(B) Thermoplastic resin (B-1) polymethylmethacrylate resin ("Sumipex" MHF, manufactured by Sumitomo Chemical Co., Ltd., weight average molecular weight 95,000, glass) (Transition temperature 115 ° C, syndiotacticity 47%)
(B-2) Polymethyl methacrylate resin (“SUMIPEX” LG35 manufactured by Sumitomo Chemical Co., Ltd., weight average molecular weight 100,000, glass transition temperature 90 ° C., syndiotacticity 39%)
(B-3) Glutaric anhydride unit-containing acrylic resin (Reference Example 1)
(B-4) Polycarbonate resin (“Taflon” # 1900 manufactured by Idemitsu Petrochemical Co., Ltd.)
(C) Impact resistance improver (C-1) Polymer obtained by Reference Example 2 (core: butyl acrylate / methyl methacrylate copolymer, shell: methyl acrylate / methyl methacrylate copolymer, refraction (Rate 1.472, Tg-30 ° C of rubber layer)
(C-2) Polymer obtained by Reference Example 3 (core: methyl acrylate / methyl methacrylate copolymer, shell: methyl acrylate / methyl methacrylate copolymer, refractive index 1.485, rubber layer Tg-34 ° C)
(C-3) Kuraray "Paraface" ME-120 (core: acrylic polymer, shell: methyl methacrylate copolymer, refractive index 1.468, Tg-50 ° C of rubber layer)
(C-4) “Metabrene” S2001 manufactured by Mitsubishi Rayon (core: silicone / acrylic polymer, shell: methyl methacrylate polymer, refractive index 1.448)
(C-5) Kaneka “Kane Ace” M511 (core: butadiene / styrene polymer; shell: methyl methacrylate polymer, refractive index 1.518, Tg-100 ° C. of rubber layer)
(C-6) “Plamate” PD-150 (polylactic acid / diol / dicarboxylic acid block copolymer, Tg 50 ° C.) manufactured by Dainippon Ink & Chemicals, Inc.
(D) Reactive compound (D-1) Glycidyl group-containing acrylic / styrene copolymer (“ARUFON” UG4040 manufactured by Toagosei Co., Ltd., weight average molecular weight 10,000)
(D-2) Glycidyl group-containing acrylic copolymer ("Marproof" G2050M manufactured by NOF Corporation, weight average molecular weight 210,000)
(D-3) Oxazoline group-containing styrenic polymer (“Epocross” RPS-1000 manufactured by Nippon Shokubai, weight average molecular weight 140,000)
(D-4) Diglycidyl terephthalic acid ester (“Denacol EX-711” manufactured by Nagase ChemteX, weight average molecular weight 260)
(D-5) Polycarbodiimide (Nisshinbo “Carbodilite” HMV-8CA, weight average molecular weight 2000).
(E) Organically modified layered silicate (E-1) Montmorillonite (E-2) colloidal silica exchanged with 12-aminododecanoic acid hydrochloride obtained in Reference Example 4 (“OSCAL” manufactured by Catalytic Chemical Industry)

[Reference Example 1] (B-2) Production of Acrylic Resin Containing Glutaric Anhydride Units A methyl methacrylate / acrylamide copolymer (with a capacity of 20 liters) and a baffle and a foudra-type stirring blade ( (Described in Japanese Examined Patent Publication No. 45-24151) A solution obtained by dissolving 0.05 part in 165 parts of ion-exchanged water was stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate suspension polymerization.
Methacrylic acid 10 parts by weight Methyl methacrylate 60 parts by weight Styrene 20 parts by weight t-dodecyl mercaptan 0.3 parts by weight 2,2′-azobisisobutyronitrile 0.4 parts by weight

  After raising the reaction temperature to 65 ° C. over 15 minutes, the temperature was raised to 100 ° C. over 50 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to the usual method to obtain a bead-shaped vinyl copolymer (b-2). As a result of measuring residual monomers by gas chromatography, the residual monomers were 0.7 parts by weight of methacrylic acid, 0.9 parts by weight of methyl methacrylate, and 0 parts by weight (not detected) of styrene.

This (b-2) is supplied from the hopper port of a vented co-rotating twin screw extruder (PCM-30 manufactured by Ikegai Iron Works) with a screw diameter of 30 mm and an L / D of 25. The resin temperature is 250 ° C. and the screw rotates. By melt extrusion at several hundred rpm, a copolymer (B-2) containing pellet-shaped glutar anhydride units was obtained. It was 135 degreeC as a result of measuring the glass transition temperature (Tg) by DSC about obtained (B-2). ^{The 1} H-NMR spectrum was measured, and the spectrum was assigned with a peak of 0 to 0.8 ppm. The hydrogen of the α-methyl group of methacrylic acid, methyl methacrylate and glutaric anhydride ring compounds, 0.8 to 1.6 ppm. The peak of is the hydrogen of the methylene group of the polymer main chain, the peak of 2.4 ppm is the α-hydrogen of styrene, the peak of 3.0 ppm is the hydrogen of carboxylic acid ester of methyl methacrylate (—COOCH ₃ ), the peak of 6.7 ppm Is the hydrogen of the benzene ring of styrene, and the peak at 11.9 ppm is the hydrogen of the carboxylic acid of methacrylic acid. As a result of calculating the composition of each copolymer unit from the integral ratio of the spectrum, it was as follows.
Methacrylic acid unit: 0.5% by weight
Methyl methacrylate unit: 67.5% by weight
Glutaric anhydride unit: 13.0% by weight
Styrene unit: 19.0% by weight.

[Reference Example 2] (Production example of impact resistance improver (C-1))
A reaction vessel equipped with a reflux condenser is charged with 120 parts by weight of deionized water, 0.2 parts by weight of potassium carbonate, 0.2 parts by weight of dioctyl sulfosuccinate and 0.005 parts by weight of potassium persulfate, and stirred under a nitrogen atmosphere. Then, a mixture of 56 parts by weight of butyl acrylate, 12 parts by weight of methyl methacrylate and 1 part by weight of allyl methacrylate was continuously added over 60 minutes, and then kept at 70 ° C. for 30 minutes to obtain a core layer polymer. Obtained. Next, after adding 0.005 part by weight of potassium persulfate, a mixture comprising 19 parts by weight of methyl methacrylate and 10 parts by weight of methyl acrylate was continuously added over 60 minutes, and kept at 70 ° C. for 60 minutes. The shell layer (second layer) was polymerized. This latex is coagulated with sulfuric acid, neutralized with caustic soda, washed with water at 50 ° C. and dehydrated three times, and the solid content is dried at 80 ° C. for 12 hours to obtain a multilayer polymer (C-1) having a two-layer structure. Of powder was obtained. Regarding C-1, the refractive index was 1.472, and the Tg of the rubber layer was −30 ° C.

[Reference Example 3] (Production example of impact resistance improver (C-2))
A reaction vessel equipped with a reflux condenser was charged with 300 parts by weight of deionized water, 1.0 part by weight of sodium stearate and 0.1 part by weight of sodium N-lauroyl sarcosinate, stirred at 70 ° C. for 30 minutes, and then persulfuric acid. After adding 0.01 parts by weight of potassium and stirring under a nitrogen atmosphere, a mixture comprising 50 parts by weight of methyl methacrylate, 2 parts by weight of methyl acrylate and 0.15 parts by weight of allyl methacrylate was continuously added over 60 minutes. It was added and held at 80 ° C. for 60 minutes to obtain a core layer polymer. Next, after adding 0.01 part by weight of potassium persulfate, a mixture consisting of 58 parts by weight of butyl acrylate, 12 parts by weight of styrene and 1 part by weight of allyl methacrylate was continuously added over 60 minutes, at 70 ° C. The shell layer (second layer) was polymerized by holding for 30 minutes. Next, after adding 0.01 part by weight of potassium persulfate, a mixture comprising 29 parts by weight of methyl methacrylate and 1 part by weight of methyl acrylate was continuously added over 60 minutes, and kept at 70 ° C. for 60 minutes. The shell layer (third layer) was polymerized. This latex is coagulated with sulfuric acid and neutralized with caustic soda, followed by washing and dehydration with 50 ° C. warm water three times, and the solid content is dried at 80 ° C. for 12 hours to obtain a three-layer multilayer polymer (C-2) Of powder was obtained. Regarding C-2, the refractive index was 1.485 and the Tg of the rubber layer was -34 ° C.

[Reference Example 4] (Production Example of Organically Modified Layered Silicate (E-1))
100 g of Na-type montmorillonite (Kunimine Industries: “Kunipia F”, cation exchange capacity 120 m equivalent / 100 g) is stirred and dispersed in 10 liters of hot water, and 30.2 g of 12-aminododecanoic acid hydrochloride (equal to cation exchange capacity, etc.) 2 L of warm water in which the amount was dissolved was added and stirred for 1 hour, the resulting precipitate was filtered off and washed with warm water three times, and the resulting solid was vacuum-dried at 80 ° C. to obtain E-1. .

  The measurement method and determination method used in the present invention are shown below.

(1) Weight average molecular weight (Mw)
It is a value of weight average molecular weight in terms of standard PMMA measured by gel permeation chromatography (GPC). Hexafluoroisopropanol was used as a solvent, the flow rate was 0.5 mL / min, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected and measured.

(2) Glass transition temperature (Tg)
About each raw material before a mixing | blending, it measured by the differential scanning calorimeter (DSC) RDC220 by Seiko Electronics. The measurement conditions are a sample 10 mg, a nitrogen atmosphere, and a temperature increase rate of 20 ° C./min.

(3) Stereoregularity A value measured by 1H-NMR measurement. 1H-NMR measurement was performed using JNM-AL400 manufactured by JEOL Ltd., using deuterated chloroform as a solvent, and a sample concentration of 20 mg / mL.

(4) Refractive index The impact resistance improver used was press-molded at 150 ° C. to form a sheet having a thickness of 0.5 mm, and then a test piece having a width of 5 mm and a length of 20 mm was cut out and an Abbe refractometer ( The refractive index at 23 ° C. and 589 nm wavelength was measured by Atago DR-M2).

(5) Transparency A 5 cm × 5 cm molded product was cut out from the center of the sheet, and the haze was measured according to JIS-K7105 using a Nippon Denshoku Industries haze meter NDH-300A.

(6) Impact characteristics A 5 cm × 5 cm molded product was cut out from the center of the sheet, and the impact strength (DuPont impact) was measured according to JIS-K7211, with a 50% fracture energy value measured at an impact radius of 6.3 mm, a load of 200 g, and a temperature of 23 ° C. Strength).

(7) Dispersion state of impact resistance improver in sheet A part is cut out from the center of the sheet, an ultrathin section is prepared using a microtome, and a transmission electron microscope (TEM) H-7100 manufactured by Hitachi, Ltd. is used. Observed at a magnification of 20,000, the primary particle diameter was measured for any 100 dispersed particles, and the average value was taken as the dispersed particle diameter. Moreover, regarding the ratio (X / Y) of the number of aggregated particles (X) and the number of unaggregated particles (Y) of the impact modifier, Hitachi Transmission Electron Microscope (TEM) H-7100 was used. Observation was performed at a magnification of 20,000 times, and for any 100 dispersed particles, the case where the dispersed particles of the impact resistance improving agent were in contact was determined as aggregated particles, and X / Y was determined.

[Examples 1-5, Comparative Examples 1-2]
A polylactic acid resin and a thermoplastic resin having a deflection temperature under load (DTUL) shown in Table 1 were melt-kneaded at a cylinder temperature of 210 ° C. using a twin screw extruder (30 mmφ) according to the blending ratio shown in Table 1, and pelletized. A resin composition was obtained. The thermoplastic resin used as a raw material and pellets obtained by melt kneading were injection-molded at a cylinder temperature of 210 ° C. and a mold temperature of 30 ° C. to produce a 127 mm × 12.7 mm × 3.2 mm test piece. Using the test piece, DTUL was measured according to ASTM method D648.

  About the obtained resin composition, the melt flow rate (MFR) in 210 degreeC and a 21.2N load was measured using the melt indexer according to JISK7210.

  Subsequently, the obtained resin composition was used as a T-die having a die width of 250 mm and a lip width of 1 mm and a cooling roll as a first roll having a surface temperature of 50 ° C., a second roll having a surface temperature of 60 ° C., and a first roll having a surface temperature of 40 ° C. By using a single-screw extruder (30 mmφ) equipped with 3 rolls, by extrusion molding at a cylinder temperature of 210 ° C., a screw rotation speed of 80 rpm, a T-die temperature of 210 ° C., an extrusion speed of 1 m / min, and a take-up speed of 1 m / min. , Created a sheet. Moreover, it determined from the electric current value of an extruder about the load (sheet preparation load) to a single screw extruder. That is, the smaller the current value, the smaller the load, and the higher the current value, the larger the load.

About the obtained sheet | seat, surface smoothness was determined visually by the following reference | standard.
A: The surface is smooth.
Δ: There are irregularities on the surface.
X: There are irregularities on the surface, and there are tears (holes).

  About the obtained sheet | seat, the thickness of the center part of the orthogonal | vertical direction was measured using the micro gauge with respect to the take-up direction of a sheet | seat. Further, a 5 cm × 5 cm test piece was cut out from the center of the obtained sheet, and haze was measured according to JIS K7105, and pencil hardness was measured according to JIS K5600-5-4.

  Further, from the obtained sheet, a test piece having a size of 10 mm × 100 mm was cut out and treated as a heat sag test at 70 ° C. for 30 minutes, and then the deformation was obtained to evaluate the heat resistance.

  Subsequently, by using a vacuum forming machine, the sheet heated under the conditions of a heating temperature of 100 ° C. and a heating time of 60 seconds is brought into close contact with the mold having a mold temperature of 40 ° C. A cylindrical container having a depth of 10 cm was obtained.

  The thickness of five arbitrary positions of the side surface portion and the bottom surface portion of the obtained container was measured with a micro gauge, and the stretched portion or the unstretched portion was confirmed from [thickness of each part of the container / sheet thickness]. That is, when [the thickness of each part of the container / the thickness of the sheet] is less than 1, it was determined to be an extended part, and when it was 1, it was determined to be an unstretched part.

  Further, the crystal melting enthalpy (ΔHm) of the stretched part was measured using DSC at a temperature rising rate of 20 ° C./min.

After the obtained container was treated at 80 ° C. for 30 minutes using a hot air dryer, the volume retention rate (%) = [volume after treatment / volume before treatment] × 100 was obtained, and heat resistance was obtained according to the following criteria. Sex was evaluated. The volume was measured by pouring water into the container to fill the container and then measuring the amount of water in the container with a graduated cylinder.
A: 90% ≦ volume retention ratio ○: 70% ≦ volume retention ratio <90%
Δ: 30% ≦ volume retention <70%
X: Volume retention <30%

  The results are shown in Table 1.

  The following is clear from the examples and comparative examples in Table 1.

  From a comparison between Examples 1 to 5 and Comparative Examples 1 and 2, a sheet made of a resin composition comprising polylactic acid and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or higher is It can be seen that the film is excellent in transparency and heat resistance. Also, the pencil hardness is excellent, and it can be said that it has sufficient scratch resistance as a container material. Moreover, it turns out that the container formed by shape | molding the sheet | seat is excellent in heat resistance, having an extending | stretching part and an unstretched part. Further, from Example 5, by using a polymethyl methacrylate resin and a glutaric anhydride unit-containing acrylic resin together as the thermoplastic resin, a sheet having excellent transparency and heat resistance can be obtained. It turns out that the container formed is excellent in heat resistance, having an extending | stretching part and an unstretched part.

  Moreover, about each container of Examples 2 and 4, and Comparative Examples 1 and 2, after putting a banana peel and cutting to about 3 cm in length, each container is shape | molded in an opening part. For this purpose, a test piece obtained by cutting out the prepared sheet into a size of 8 cm × 8 cm was set as a lid so that there was no gap between the opening and left at 30 ° C. When the contents were visually observed after 2 days, there was almost no discoloration in Example 4, slight discoloration in Example 2, and considerable discoloration in Comparative Examples 1 and 2, and the container of the present invention was fresh. It was found that the retention was excellent.

[Examples 6 to 9]
When melt kneading a polylactic acid resin and a thermoplastic resin having a deflection temperature under load (DTUL) shown in Table 2 in accordance with the blending ratio shown in Table 2, either a single screw extruder (40 mmφ) or a twin screw extruder (30 mmφ) A pellet-shaped resin composition was obtained in the same manner as in Example 1 except that these were used. In addition, DTUL and MFR were measured in the same manner as in Example 1 for the thermoplastic resin used as a raw material and the resin composition obtained by melt kneading.

  Then, the sheet | seat was created similarly to Example 1 except setting the surface temperature of a cooling roll as shown in Table 2 using the obtained resin composition.

  In the same manner as in Example 1, the sheet creation load, sheet characteristics (surface smoothness, thickness, haze, pencil hardness and heat resistance), and container characteristics (thickness of each part, ΔHm, heat resistance) were evaluated.

  The results are shown in Table 2.

  From the examples of Table 2, the following is clear.

  From the comparison of Examples 6 to 9, after melt-kneading polylactic acid and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or higher, extruding from a die and cooling and solidifying at 40 to 70 ° C. It can be seen that the sheet obtained by this is excellent in surface smoothness, transparency and heat resistance. Also, the pencil hardness is excellent, and it can be said that it has sufficient scratch resistance as a container material. Moreover, it turns out that the container formed by shape | molding the sheet | seat excellent in surface smoothness is excellent in heat resistance, having an extending | stretching part and an unstretched part. In addition, in the sheet | seat with an unevenness | corrugation on the surface, when shape | molding a container, since the tear generate | occur | produced in the container and the container of a favorable shape could not be obtained, the container characteristic evaluation could not be performed. As for melt-kneading, a sheet having excellent transparency can be obtained by using a twin-screw extruder, and the container formed from the sheet has heat resistance while having stretched parts and unstretched parts. It turns out that it is excellent.

[Examples 10 to 11]
A pellet-shaped resin composition was obtained in the same manner as in Example 1 except that the polylactic acid resin and the thermoplastic resin having a deflection temperature under load (DTUL) shown in Table 3 were in accordance with the blending ratio shown in Table 3. In addition, DTUL and MFR were measured in the same manner as in Example 1 for the thermoplastic resin used as a raw material and the resin composition obtained by melt kneading. Moreover, about the polymethylmethacrylate used as a raw material, stereoregularity (syndiotacticity) was measured using DSC using Tg and 1H-NMR.

  Subsequently, using the obtained resin composition, a sheet was prepared in the same manner as in Example 1, and the load at the time of sheet creation and sheet characteristics (surface smoothness, thickness, haze, pencil hardness and heat resistance) were evaluated. did. Moreover, the sample was cut out from the obtained sheet | seat and the stereoregularity (syndiotacticity / isotacticity) of the polymethylmethacrylate in a sheet | seat was calculated | required by 1H-NMR measurement.

  Subsequently, container characteristics (thickness of each part, ΔHm, heat resistance) were evaluated in the same manner as in Example 1 using the obtained sheet.

  The results are shown in Table 3.

  From the examples and comparative examples in Table 3, the following is clear.

  From Examples 10 and 11, a sheet made of a resin composition obtained by blending polylactic acid and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or higher is excellent in transparency and heat resistance. I understand. Also, the pencil hardness is excellent, and it can be said that it has sufficient scratch resistance as a container material. In addition, as a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or higher, a sheet having particularly excellent heat resistance is obtained when two types of polymethyl methacrylate are used in combination, and the sheet is molded. It turns out that a container is excellent in heat resistance, having an extending | stretching part and an unstretched part.

[Examples 12 to 18, Comparative Example 3]
A pellet-shaped resin composition was obtained in the same manner as in Example 1 by using a polylactic acid resin, a thermoplastic resin having a deflection temperature under load (DTUL) shown in Table 4, and an impact resistance improver according to the blending ratio shown in Table 4. It was. In addition, DTUL and MFR were measured in the same manner as in Example 1 for the thermoplastic resin used as a raw material and the resin composition obtained by melt kneading. Moreover, about the polymethylmethacrylate used as a raw material, stereoregularity (syndiotacticity) was measured using DSC using Tg and 1H-NMR.

  Subsequently, using the obtained resin composition, a sheet was prepared in the same manner as in Example 1, and the load during sheet preparation and sheet characteristics (surface smoothness, thickness, haze, and heat resistance) were evaluated. Moreover, the impact strength was measured according to JIS-K7211. Furthermore, the dispersion state of the impact modifier in the sheet was observed using a TEM.

  Subsequently, container characteristics (thickness of each part, ΔHm, heat resistance) were evaluated in the same manner as in Example 1 using the obtained sheet.

  The results are shown in Table 4.

  The following is clear from the examples and comparative examples in Table 4.

  From Examples 12 to 18 and Comparative Example 3, comprising a resin composition comprising a polylactic acid resin, a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa, of 75 ° C. or more, and an impact resistance improver. It can be seen that the sheet is excellent in transparency, heat resistance and impact resistance. Further, from Example 18, a sheet having particularly excellent heat resistance is obtained when two types of polymethyl methacrylate are used in combination as a thermoplastic resin having a deflection temperature under load of 75 ° C. or higher measured at a load of 1.82 MPa. It can be seen that the container formed by molding is excellent in heat resistance while having a stretched part and an unstretched part.

[Examples 19 to 32, Comparative Example 4]
Example 1 A polylactic acid resin, a thermoplastic resin having a deflection temperature under load (DTUL) shown in Tables 5 and 6, an impact resistance improver, a reactive compound and inorganic particles according to the blending ratios shown in Tables 5 and 6 In the same manner as above, a pellet-shaped resin composition was obtained. For Example 31, a polylactic acid resin, a thermoplastic resin having a deflection temperature under load (DTUL) shown in Tables 5 and 6, and inorganic particles were stirred and mixed in tetrahydrofuran for 3 hours and added to a large excess of ethanol. The precipitate obtained later was dried at 70 ° C. to obtain a powdery resin composition. Further, DTUL and MFR were measured in the same manner as in Example 1 for the thermoplastic resin used as a raw material and the resin composition obtained by melt kneading. Moreover, about the polymethylmethacrylate used as a raw material, stereoregularity (syndiotacticity) was measured using DSC using Tg and 1H-NMR.

  Subsequently, using the obtained resin composition, a sheet was prepared in the same manner as in Example 1, and the load during sheet preparation and sheet characteristics (surface smoothness, thickness, haze, and heat resistance) were evaluated. Moreover, the impact strength was measured according to JIS-K7211. Furthermore, the dispersion state of the impact modifier in the sheet was observed using a TEM.

  Subsequently, container characteristics (thickness of each part, ΔHm, heat resistance) were evaluated in the same manner as in Example 1 using the obtained sheet.

  The results are shown in Tables 5 and 6.

  The following is clear from the examples and comparative examples in Tables 5 and 6.

  From Examples 19 to 32 and Comparative Example 4, in addition to the polylactic acid resin, a thermoplastic resin having a deflection temperature under load of 75 ° C. or higher measured at a load of 1.82 MPa, an impact resistance improver, a reactive compound and inorganic particles were added. It can be seen that a sheet made of a resin composition that is appropriately selected and blended is excellent in transparency and heat resistance, and in a preferred embodiment, is excellent in impact resistance. Further, from Examples 20 to 22 and 29 to 32, a sheet having particularly excellent heat resistance when two kinds of polymethyl methacrylate are used in combination as a thermoplastic resin having a deflection temperature under load of 75 ° C. or higher measured at a load of 1.82 MPa. It can be seen that Further, Examples 23 to 28 and 32 show that a sheet having excellent impact resistance can be obtained when an impact resistance improver is blended. Further, from Examples 29 to 32, when inorganic particles are blended, a sheet particularly excellent in heat resistance is obtained, and a container formed by molding the sheet has excellent heat resistance while having stretched parts and unstretched parts. I understand that.

Claims (11)

A sheet comprising a polylactic acid resin having a thickness of 0.3 mm or more and a haze of 10% or less, comprising a resin composition comprising a polylactic acid resin and a thermoplastic resin having a deflection temperature under load of 752 ° C. measured at a load of 1.82 MPa. . The sheet containing the polylactic acid resin according to claim 1, wherein the thermoplastic resin is polymethyl methacrylate. Weight ratio of the polylactic acid resin and the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or more (polylactic acid resin / heat at which a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or more. The sheet containing the polylactic acid resin according to claim 1 or 2, wherein the plastic resin is 55/45 to 10/90. The sheet | seat containing the polylactic acid resin of any one of Claims 1-3 whose load deflection temperature measured by the load of 1.82 MPa of the said resin composition is 65 degreeC or more. A polylactic acid resin characterized by being melt-kneaded with a polylactic acid resin and a thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa of 75 ° C. or higher, extruded from a die, and cooled and solidified at 40 to 70 ° C. A method for producing a sheet including the same. 6. The method for producing a sheet containing a polylactic acid resin according to claim 5, wherein melt kneading is performed using a twin screw extruder. The method for producing a sheet containing a polylactic acid resin according to claim 5, wherein the thermoplastic resin is polymethyl methacrylate. Weight ratio of the polylactic acid resin and the thermoplastic resin having a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or more (polylactic acid resin / heat at which a load deflection temperature measured at a load of 1.82 MPa is 75 ° C. or more. The manufacturing method of the sheet | seat containing the polylactic acid resin of any one of Claims 5-7 melt-kneaded in the range of 55 / 45-10 / 90. The stretched part which shape | molds the sheet | seat containing the polylactic acid resin in any one of Claims 1-4, or the sheet | seat containing the polylactic acid resin obtained by the manufacturing method in any one of Claims 5-8, and unstretched Of manufacturing a container having a portion. An extending portion obtained by molding a sheet containing the polylactic acid resin according to any one of claims 1 to 4 or a sheet containing the polylactic acid resin obtained from the production method according to any one of claims 5 to 8; A container having an unstretched portion. The container according to claim 10, wherein the crystal melting enthalpy of the stretched portion is 5 J / g or more.