TW200424260A - Biodegradable polyester resin composition, method for producing same, foam material and product made from same - Google Patents

Abstract

This invention provides a biodegradable polyester resin composition and a method for producing same, said resin composition has excellent gas barrier property, mechanical strength, heat-resisting property, and a suitable rheology property for forming the foam material. The biodegradable polyester resin composition contains 100parts of biodegradable polyester resin containing hydroxycarbonic acid unit more than 50 mole%, 0.01-10 mass parts of (metha) acrylic ester compound, and 0.05-20 mass parts of bedded silicate.

Description

May, the invention said a month [Technical field to which the invention belongs] B The present invention is related to superior mechanical strength or heat resistance, no operability, and is conducive to the fluid flow characteristics of foam or product molding, and the gas barrier is also superior The biodegradable polyglyceride is used to save money, its manufacturing method, and foams and products made from the composition. [Prior technology] Compared with other biodegradable resins, polylactic acid has the characteristics of high melting point and excellent heat resistance. The material has low viscosity. For example, when the bubble is extruded, the bubble will rupture, and a sufficient expansion ratio cannot be obtained. The bubble is uneasy during plastic molding or blow molding. Problems, forming conditions are strictly limited. 71, soil — called 々, 格, 格, 格, 格, 格, 日, 日, 日, 日, 日, 日, 日, 日, 日, 有, and 有 have the disadvantages of poor production efficiency such as injection molding. Therefore, in order to be practical, it is necessary to improve the performance of strain hardening at the time of melting viscosity and tensile viscosity, and to increase the crystallization speed. Sorry, the recipe is secretive, and the method of adding a polymer with a high degree of polymerization or using a polymer having a long-chain branch is effective. However, in the production of a polymer with a high degree of polymerization, not only long-term polymerization is required, productivity is deteriorated, but due to long-term heating, phenomena such as coloring or dissolution can be seen. Therefore, for example, a biodegradable polyester having a weight average molecular weight of 500,000 or more is not practical. On the other hand, although a method for manufacturing a long-chain branched polylactic acid is known as adding a second polyfunctional initiator during polymerization ^ (JP-A-I0-7778, JP-A-2000-136256), If the chain is introduced / introduced, there will be failures such as resin removal, and the degree of branching will be inadvertent. 3J4679 5 Problems such as changes α and 'Also discuss the method of mixing and mixing layered sulfonium salts in JP-A-2001 -89646 reveals that organic layered clay minerals are made into an average particle size of 1 // m or less, and are melt-kneaded with resin to obtain a resin with high rigidity and improved biodegradability. However, this document does not specifically describe why layered clay minerals are made to have an average particle size of less than m. It also does not describe the various conditions at the time of forming, and it is unknown whether the formability is improved. On the other hand, a method is known in which a biodegradable resin is produced by melt-kneading with a peroxide, a reactive compound, or the like to cause cross-linking and exhibit strain hardening. This method is simple and extensively studied for the point that the degree of branching can be freely changed. However, the acid anhydride or polycarboxylic acid used in JP-A-11-60928 is not practical because it is prone to non-uniform reactivity and requires reduced pressure. In addition, the polyisocyanates used in JP-B-2571329 or JP-A-20〇 (M 7037, etc.) are liable to decrease in molecular weight when remelted and have problems in safety during handling, etc., and technologies for achieving practical levels have not yet been established. JP-A-10-324 766 discloses that if a biodegradable polyester resin synthesized from a dibasic acid and a diol is combined with an organic peroxide and a compound having an unsaturated bond and cross-linked, it can be effectively foamed. This method is an example of a method in which these crosslinking agents are contained in resin fine particles at a temperature lower than the W point of the resin. 'Although the use of monoethylbenzene as a crosslinking assistant is described in detail', Base) acrylate compounds have not been discussed 'only the application of biodegradable polyester resins with low heat resistance synthesized from dibasic acids and glycols is discussed. Moreover, the addition of such crosslinking agents or cross-linking It is a method that can be operated stably for a long period of time. 6 It is known to use m or W-based slow acid units as the main body to provide decomposable polyvinegar. However, the biodegradable polymer is crystallized = 1 'injection molding Poor operability in various forming processes Disadvantages. Insufficient. The method of adding inorganic fine powder, but it does not have the gas barrier properties of the knife, especially the lack of oxygen barrier. So far, it cannot be used for foods that require gas barrier properties. θ Improves gas barrier properties by dispersing layered fossilate in the resin :::. Proposal. It is recognized that the gas component is passed through the layered silicate in the resin, I, bypassing the layered stone The acid salt advances to increase gas barriers. For example, Yu Yun 4552 revealed the effect on polyamic acid resin, and Yu Xin revealed that it is applied to aliphatic polys. However, only layered stone Xi = salt mixed domain lipids can be obtained. The problem is that the fluid flow characteristics of various moldings are poor, and the operability is poor. It has excellent mechanical strength or heat resistance, and is good for foams or biodegradable foams made of the composition. The present invention provides To solve the above problems, the more rapid the crystallization speed, the operability problem and the gas-barrier properties of the resin composition, the manufacturing method, the use and the product of the button forming, there is no problem with the operation. The As a result, the present invention has been continuously researched to complete the present invention. That is, the present invention is based on 100 parts by mass of a biodegradable polyacetate resin containing 50 mol% or more of _ and / or / 5-hydroxycarboxylic acid units, A biodegradable polyester resin composition having a content of (methyl) acetic acid compound of 〇01 to 10f and a layered oxalic acid 3J4679 7 I 0.05 to 20 parts by mass is used as the gist. The method for manufacturing the biodegradable polyester resin composition of the present invention is that the layered silicate and the biodegradable polymer resin composition are melt-kneaded, and the (fluorenyl) acrylate compound and peroxide or It is a solution or dispersion of a (fluorenyl) acrylate compound or a solution or dispersion of a (meth) acrylate compound and a peroxide, and melt-kneading is the main point. The present invention is directed to a biodegradable resin foam obtained by foam-molding the biodegradable polyester resin composition of the present invention. The present invention is directed to a biodegradable resin product formed by subjecting the biodegradable polyester resin composition of the present invention to any one of injection molding, extrusion molding, and blow molding. [Embodiment] The biodegradable polyester resin composition of the present invention must be a specific composition containing a biodegradable polyester resin, a (meth) acrylate compound, and a layered silicate. Compounding a (fluorenyl) acrylate compound with a biodegradable polyester resin with excellent heat resistance can increase the crystallization speed and improve the formability. However, if 疋 'is blended with only a (meth) acrylic acid ester compound, the rigidity during heating is low, and sufficient operability cannot be obtained. In the present invention, in addition to the (fluorenyl) acrylate compound, a layered silicate is also added, which can be used to improve the melt viscosity, show strain hardening in the measurement of tensile viscosity, improve rigidity during heating, and have good operability. A resin composition with excellent 8 314679 < In addition, the combination of layered silicates can improve mechanical properties or dimensional stability at the same time as improving the resistance and growth. In addition, the gas barrier properties, especially the oxygen barrier properties, are further improved. The biodegradable polyester resin composition of the present invention constituted as described above is a composition having high melt viscosity, excellent strain hardening property in the measurement of tensile viscosity, and fast crystallization speed. However, these effects cannot be obtained simply by a composition in which a biodegradable polyester resin is mixed with a (fluorenyl) acrylate compound and a layered silicate. In the present invention, production of the biomeal horny polyvine resin composition constituted as described above through the manufacturing method of the present invention can solve the problem of operability, and the obtained product has excellent heat resistance or mechanical strength and good appearance. This will be described in detail below. The biodegradable polyester resin composition of the present invention must contain 100 parts by mass of a biodegradable polyester resin containing 50 mol / 6 or more of α- and / or bis-based diacid units, (fluorenyl) acrylate Compounds 0.01 to 10 parts by mass and layered silicates 0.05 to 20 parts by mass. As the main component, the biodegradable polyester resin must contain α- and / or tribasic acid units of 50 mol% or more. And / or if the content of the tenaconic acid unit is less than 50 mol%, the biodegradability or heat resistance will decrease. The α- and / or; 9-acrylic acid units include D · lactic acid, L-lactic acid, or a mixture of these, glycolic acid, 3-hydroxybutyric acid, valproic acid, 3-hydroxyhexanoic acid, and the like. Among them, biodegradable polyester resins containing D-lactic acid, l-lactic acid, or a mixture thereof are more preferable because they have superior mechanical strength or heat resistance. In the present invention, the resin composition contains 50 mol% of polylactic acid, polyacetic acid, poly (3-butyric acid) acid), and poly (3-hydroxyhexanoic acid). , Hengong Tuwu) 0 Xuansi copolymer or mixture is preferred.

Human, and Guangming biodegradable polyester resins can be melt-polymerized by the commonly known < " > method or more in combination with solid-phase polymerization. 3- The biodegradable polyethylene glycol of the present invention is in a range that does not significantly impair the heat resistance of α_ and / or “based diene acid”, and can also be copolymerized or mixed with it if necessary. Other biodegradable resins can be made of water (ethylene succinic acid) or poly (butylene succinic acid), etc. $ Representative: aliphatic polyvinegar composed of alcohol and tartaric acid, and polycaproline Western purpose) is representative of poly (ω-jingjiyaozhi purpose) Even if it contains, aromatic components, it also shows biodegradable (butylene succinic acid acetic acid-butylene terephthalate) copolymer or (butylene Adipic acid-butylene terephthalic acid purpose) copolymers, polyamines, poly, starch, and other polysaccharides, etc. The molecular weight of the biodegradable polymer resin of the present invention is not particularly limited. It is more preferable to be more than 50,000 to less than 1 million. More preferably to be more than 100,000 to less than 1 million. If the weight average molecular weight is less than 50,000 The melt viscosity of the resin composition will be too low and unfavorable. If the weight average molecular weight exceeds 1 million, the moldability of the resin composition will decrease sharply and unfavorably. ^ The (meth) acrylate compound of the present invention is High reactivity with biodegradable resins, monomers are not easy to remain, toxicity is small, and resin color is less, so it has 2 or more (fluorenyl) propenyl groups in the molecule or has more than 1 (fluorenyl) propenyl groups Compounds with one or more glycidyl or vinyl groups are better than 314679 10. Specific compounds include glycidyl fluorenyl acrylate, glycidyl acrylate, glycerol difluorenyl acrylate, and tris (fluorenyl) Propane Trimethyl Acrylate, Trihydroxymethyl Propane Triacrylate, Diluted Propoxy Polyethylene Glycol Monoacrylate, Allyloxy Polyethylene Glycol Monomethyl Acrylic Acid Propylene glycol ester, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, polybutylene glycol dimethacrylate. These alkanediols can be listed in various lengths Alkylene copolymer , Butanediol methacrylate, butanediol acrylate, etc. The compounding ratio of the (fluorenyl) acrylate compound of the present invention must be 0.01 to 10 parts by mass for 100 parts by mass of the biodegradable polystyrene resin. 〇 Knife 0 to 5 parts by mass is preferred. If the compounding ratio of the (meth) acrylate compound is less than 0.01 parts by mass, the mechanical strength of the object of the present invention cannot be obtained, and the thermal properties and dimensions are determined. The improvement effect of white, if the compounding ratio of (meth) acrylate compound 2 exceeds 10 parts by mass, the degree of cross-linking will be too strong, and the operability will change. Two: two = blending in the biodegradable polymer resin)) Acrylic acid esterification product The right combination of peroxides is easy to express and is better. For example, specific examples of strain-hardening k emulsions such as 醯, bis (butyl peroxide) J 歹, etc. are given; * Base bis (butyl peroxide) cyclodecahydrate and (butyl peroxide) butyl pentoxide, benzamidine, lice-isopropylbenzyl, percumene, -methyl-emulsified dibutyl, Bis (butyl peroxide) di-f-based di (peroxidation Butyl) hexyne, perfluoro-methyldi (peroxy) For biodegradability, take τ-based alkene. Compounding ratio of peroxide "Resin" 00 parts by mass of 0.02 to 2 "314679 11 is more preferred, and 0.05 to more than 20 parts by mass is even better. The blending ratio of peroxide will decompose when mixed with the resin, but it is not good for cost. In addition, peroxides are not good in the obtained resin composition. For example, the layered sand of the present invention has problems even when used in combination. It is necessary that the shape of the spartate gg lipid _ mass part is; The proportion of 5 is better for the amount of biodegradable polyacetate. Layered silicon .: 5 to 20 parts by mass, not enough to obtain from 0.1 to 10 parts: If the blending ratio is less than 0.05 parts by mass, the parts will become brittle and unfavorable: Degree or heat resistance, etc., if it exceeds 10 parts by mass Body blocking, but even with 10. The second combination of layered fossilates can enhance gas variability. Above the Bailey knife, the effect is hardly a specific example of layered silicate, such as mica. Examples of montmorillonite include montmorillonite: stone, warp stone, and swelling aerobic stone. Examples of swelling properties of prime mica can be Lexington:;, montmorillonite, mica with bell, mica with bell, etc .; in addition to this; Guangsi stone mica, sodium pearl mica, _, such as:; = Use: Water hydrazone, which is a layered stone that is used to improve the gas-barrier property. Montmorillonite and swollen fluoromica: salt with a large aspect ratio is better than ^ Gansi 1 and swelled fluoromica is better. 'Layered oxalate can be natural or synthetic Product. The synthetic product can be produced by any method such as a melting method, an internal collection method, and a hydrothermal method. These layered fossilates can be used alone or in combination of two or more minerals of different types such as 'origin, Peng method, and particle size.' The layered fossilate of the present invention is preferably one which has been previously treated with an organic cation. Examples of organic cations include protonation records of grades i to 3 amines. 314679 12 Hafnium ions such as hafnium, 4th ammonium ion, hafnium ion. Examples of the primary amine include octylamine, undecylamine, and stearylamine. Examples of the secondary amine include dioctylamine, methyloctadecyl, and octadecylamine. Examples of the tertiary amine include trioctylamine, dimethyldecan and amine mono-undecyl monofluorenamine. Examples of grade 4 ammonium ions include tetraethylene octadecyltrimethylammonium, dimethyl di-octadecyl ammonium, dihydroxyethyl octadecylhydrazone, and methyl dodecyl bis (polyethylene glycol) ammonium. , Methyl diethylene glycol) ammonium and the like. Examples of the scale ion include tetraethyl scale, tetrabutylphosphonium, dialkyltributyl scale, tetrakis (methyl) phosphonium, and 2-methylethyltriphenyl tweezers. Among these are dihydroxyethylfluorenyl octadecandite T terbium octamonium octamonium, methyl dodecyl triphenyl A ^ yldiethyl (polypropylene glycol), 1 or more layered affinity treated with basic iron ions. A = "Purpose resin, especially biodegradable polyresin resin, in order to improve the dispersibility of the layered silicon salt. Special organic phase. $ 簟 Organic The cations can be used alone, and can be used in combination on the Haisi Temple. The layered silicate is used to disperse the layered salt in the water with the above organic cations. The two methods can be listed as the form of the salt. The above organic cations are mixed by mixing the 1 H 0 organic cations of the layered silicic acid with "，, σ ，, and raw materials by stirring, and the use of layered oxalic acid is performed; said in 1 net · Method of drying. / Collectable leaves can be used in order to ridge in the polymerization. Α The sculpting property of the month is also 0.01 parts by mass; the biodegradable polyester resin 100 berices is preferably 0.01 to 10 parts by mass. Compatible with 5 parts by mass of the pot tree: "Over] ° parts by mass, the biodegradable U said, and the heat resistance or mechanical agent of the product can be used with the polymer resin, especially biodegradable :: Decrease. Compatibility ~ XK ester resin and layer 334679] 3 Polyepoxides, aliphatic polyesters, polyalcohols, polybasic acid esters and other compounds with affinity between silicate. Polyepoxy Examples of the compounds include polyisocyanate, polypropylene glycol, polybutylene glycol, and copolymers thereof. It is also possible to block 1: 2 terminal hydroxyl groups with alkoxy groups, or via monocarboxylic acid or dicarboxylic acid: Esterification. Examples of aliphatic polyesters include polylactic acid, polyglycolic acid (3-light butyric acid), poly (3-trivaleric acid), poly & caproic acid), etc. _ Glycolic acid, poly (u-caprolactone) or (polyalkylene represented by pentamole), poly (ethylene succinate), poly (butylene succinate), (butylene soil ί white acid vinegar-butadiene p-adipic acid copolymer) represented by diols and acetic acid; aliphatic polyacetates, etc. composed of fatty polyesters. Alternatively, the fluorene may be replaced by a diol. Examples of the polyhydric fluorene include esters of industrial glycerol and fatty acids such as glycerol monoglyceride, diglyceride, triglyceride, glycerol vinegar such as glutamate, pentaerythritol vinegar, etc. Examples include: citrates such as lemon :: tributyl ester or tributyl acetate citrate, etc. The above-mentioned compatibilizers have a boiling point above 25 (rc is preferred. If the boiling point is above 25 CTC, then at Gas is generated during the molding or bleeds from the obtained molded product. The number average molecular weight is preferably in the range of 2000 to 50, and more preferably 500 to 20,000. If the molecular weight is less than 2000, In the process of molding, gas is easily generated or exuded from the obtained molded product, which damages the mechanical strength or heat resistance of the product. If _5M⑽ ', the effect of improving the layered material / dispersibility tends to be small. Addition of miscibility agent Methods may include a method of directly treating the above compound in advance with a layered fossilate, a method of removing water or an organic solvent through a liquid, etc. after mixing the compounds in the presence of water or an organic solvent. Melting of polymer resin and layered silicate The method of adding during kneading and the method of adding together with the layered silicate during the synthesis of the polyresin, etc., are preferably a method of mixing with the polyester and performing a mixing treatment on the layered silicate in advance. The physical phase of the layered silicate in the biodegradable polyester resin is in the state of layered silicate. The layer is completely peeled off. The average thickness of the acid salt is 1 to 100_, preferably, more preferably! Silicon: It is preferably 1 to 2 °. Please use the X-ray diffraction to observe the layer-to-layer distance of the salt. 2.5_ or more, more preferably 3 or more thin, Γ is more than 4, please, the most ideal is that no peaks from the distance between the layers can be observed. In these layered silicate training methods, the method of mixing buildings can be changed. For example, if it is mixed with polar groups, etc., if you add a layered silicate on the / ^ ^ chemical agent, when the resin is introduced, and when the water is small, you can create a step-by-step dispersion and try to improve the gas blocking. Sex. Come in! The strain-hardening coefficient of the biodegradable polyacetate resin composition of ≧ 5 is preferably U to% if the coefficient of strain hardening is less than two. Strain-hardened products are prone to stringency. "Blistering will cause liquid bubble rupture during forming, and it is easy to produce 1 = Hook: If the strain hardening coefficient exceeds 50, the chemical conversion coefficient will greatly decrease as shown in Figure 1. The ~ 7F 'obtained from strain hardened elongation viscosity is a logarithmic plot of the tensile elongation viscosity at the high-order temperature measurement of the melting point until the drawing occurs, and the inclination 31 and After the inflection point, the ratio of the slope a2 (a2 / a)). 314679] 5 The crystallization rate index of the biodegradable polyester resin composition of the present invention is preferably 30 (minutes) or less. The more the value of the crystallization rate index is, A smaller value means a faster crystallization rate, and a larger value means a slower crystallization rate. Specifically, as shown in Figure 2, a differential scanning calorimeter (DSC) device is used to set the resin at 2 times. 〇〇r melts, from this melting state to isothermal crystallization at 130 ° C, the time (minutes) to reach the final reached degree of daily chemical degree (0) 2 to 1 knife. Crystallization speed If the index is higher than 30 (minutes), Many times, the shape of the desired product cannot be obtained, the cycle time for injection molding, etc. becomes longer, and the productivity is deteriorated. In addition, since the crystallization speed is too fast, the moldability is deteriorated, so the lower limit of the crystallization rate is about 0. (丨) is better. The crystallization rate index becomes smaller with the increase of the dose: and / or the amount of peroxide, which can make the crystallization rate: fast. In addition, the layered silicate is added. More than 2 parts can increase the crystallization 2 = degree. By adding inorganic fine powder such as talc or calcium carbonate ^ = 5 mass%, the crystallization speed can be increased due to the multiplication effect. The more functional groups of the cross-linking agent, the better The faster the crystallization speed. The composition of the biodegradable polyacetate resin can be obtained by biodegrading the polymer resin with the (meth) acrylic acid compound and the layered oxalate. It is obtained by melt-kneading by a counter-machine. Once the melt-kneading is performed, it will be difficult to present strain hardening. In the present invention, it is indicated that mm is producing biodegradability Dissolving or dispersing liquid of polyester at the same time beforehand = methyl) acrylic The acid-vinegar compound-like oxalate salt is subjected to refining. The biodegradable polyester resin and the layer 3] 4679 16 are described in detail below. The method for producing the biodegradable polymer resin composition of the present invention is to first The decomposable polyacetate resin and the layer are firstly put into a kula λ Λ / 夂 wind yttrium machine or using a quantitative feeder from the vicinity of the entrance of the kneader for kneading. 〃 Connect S and put it in the middle of the kneader ( The methyl) acrylic acid compound is melt-kneaded, and it is better to use the emulsified product at the same time. The peroxide is a solid moon solid feeder, which is supplied by a pressurized system when it is a liquid. Or it is injected ( A solution or dispersion of a meth) acrylic acid compound. In the present invention, if a (meth) acrylic acid compound and / or a peroxide is dissolved or dispersed in a medium and injected into a kneader, the operability is expected to change. Outstanding success. In other words, 'the biodegradable polyester resin and the peroxide are injected into the melt-kneading solution of a (fluorenyl) acrylic δ compound, and the biodegradable polyacetate resin is injected into the melt-kneading solution. (Meth) acrylic acid vinegar compounds and peroxides are preferably melt-kneaded by rolling from the base to the base liquid, the noble liquid, or the noble liquid. A medium for dissolving or dispersing a (meth) acrylate compound and / or a peroxide may be used. -Generally, there is no particular limitation, but it is a plasticizer excellent in compatibility with the aliphatic polyacetate of the present invention. Better, and biodegradable. For example, one or more types selected from the group consisting of aliphatic polybasic acid derivatives, aliphatic polyhydric alcohol vinegar derivatives, aliphatic oxygenated derivatives, fats, and poly-derivatives, such as aliphatic polyether polybasic acid derivatives Plastics, etc. Specific compounds include dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, ethyl acetolide, methyl acetophenate, polyacetate Ethylene glycol, dibutyl diethylene glycol succinate, and the like. The amount of the plasticizer used is preferably 30 parts by mass, 17 3146Ί9 or less, for 100 parts by mass of the resin, and more preferably (M to 20 parts by mass. The plasticizer may not be used when the reactivity of the crosslinking agent is low, but the reactivity When it is high, it is better to use more than 0m parts by mass. Also, ((meth) acrylic acid vinegar compound and peroxide can be injected separately. To make the mixing state better, it is better to use a biaxial press. Mixing temperature It is preferably in the range of (the melting point of the resin +5.0) to (the melting point of the tree moon purpose + 10.0) '-the refining interval is preferably 20 seconds to 30 minutes. The temperature or time is lower or shorter than this range If the kneading or reaction is insufficient, the resin may be decomposed or colored at high temperature or for a long time. The biodegradable polyacetate resin composition of the present invention may be made of ) Acrylic acid vinegar compounds, peroxides, and layered oxalates are used as raw materials. These melt-kneaded materials can be produced. The peroxide is decomposed during melt-kneading, and the obtained resin composition is not necessarily contained. Oxides, and added with (fluorenyl) acrylic acid Although it is better to use media such as plasticizers when peroxides are used, it is not necessary to contain the media in the product. Therefore, the resin composition of the present invention is a biodegradable flat dagger. Its characteristics are not too resistant. Pigments, heat stabilizers, oxidation inhibitors, agents, lubricants, release agents, antistatic agents such as a μ ^% ^,… J or anti-gasification agents can be added. Restrictions ... Hybrid compounds, hindered amines, sulfur compounds, copper compounds, halides of alkali metals, or mixtures of these compounds, #Hai Si. Inorganic filling materials can make oxygen: /, sulfonic acid, zinc carbonate, stone Evening limestone, dioxin, oxidative oxidation, Pingfeihua Town, Liuma 'Shaozhizhi, slang words, _ acid sodium, Liuzhen,

31461Q 18 glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite 'hydrotalcite, eight fiber, metal whisker, ceramic whisker, potassium titanate, nitrided butterfly, stone black, broken glass fiber, carbon fiber, etc. . Examples of the organic filler include starch, weaving micro-particles, wood flour, hemp, rice bran, wheat bran and the like. The biodegradable polyester resin composition of the present invention is mixed with the above-mentioned additive or other thermoplasticity. There is no particular limitation on the method of the resin: Example: After normal heating and melting, a conventional mixing method such as a uniaxial extruder, a biaxial extruder, a roll kneader, a bula mixer, etc. is used. Perform the mixing. It is also effective to use a static mixer or an electric mixer in combination. = The above additives or other thermoplastic resins can also be added during the polymerization of the decomposable resin. The general foaming method for producing a foam from the biodegradable polyester resin composition of the present invention is applicable. For example, using an extruder, a decomposable foaming agent which is decomposed at the resin melting temperature is blended with the resin in advance, and can be extruded from a slit nozzle into a sheet shape, and extruded from a circular nozzle into a monofilament shape. Examples of the decomposable foaming agent include azo compounds represented by azodimethanamine or barium azo-acid, and nitroso represented by N, N, -dinitrosopentamethylenetetramine. Compounds such as 4,4, -hydroxybis (benzenesulfonyl hydrazine) or hydrazine hydrazine carboxylate are representative hydrazine compounds or inorganic foaming agents such as sodium bicarbonate. In addition, a volatile foaming agent may be injected from the extruder and foamed. Examples of the blowing agent at this time include inorganic compounds such as nitrogen, carbon dioxide, and water; various hydrocarbons such as methyl alcohol, ethyl alcohol, and butylene; fluorine compounds; and organic solvents such as ethanol and methanol. It is also possible to change the temperature or pressure by using fine particles of resin group 19 314679, which have been prepared in advance, and impregnated with agents or water. The specific use of the board made by the extrusion foaming method is in addition to the original bent for the processing of bento boxes, various cosmetic cases, and for food container plates or cup materials, mannequins, toys, etc. It is used for various cushioning materials, biodegradable foamed sheets or foams made of foamed microparticles using 0 organic solvents containing the foaming agents shown above, or used for cosmetic boards or various paperboards. In addition to folding or cushioning materials, compression can also be carried out. Foaming microparticles for interior decoration such as kettles or cars can be molded. They can also be used as cushioning materials in their original state. Foam sheet or foam board is subjected to deep extrusion such as vacuum forming, pressure forming and vacuum pressure forming, etc. = 'manufacturable food containers, agricultural # • gardening containers, foam filling containers, and pressure filling containers, etc. . The deep extrusion forming temperature and heat treatment temperature are preferably from (Tg + 20 ° C) to (Tm-2 (TC). If the deep extrusion temperature is less than (Tg + 20 ° C), deep extrusion is difficult, so Insufficient heat resistance of the obtained container 'If the relative deep extrusion temperature exceeds (Tm-20 ° C), thickness unevenness will occur, orientation collapse, and impact resistance will decrease. Next, the biodegradable polyester resin from the present invention The extrusion molding method used when the composition is manufactured into an extruded product will be described. The extrusion molding method may use a T die method and a round die method. The extrusion molding temperature needs to be at the melting point (Tm) of the biodegradable polyester resin composition. ) Or above the flow start temperature, preferably 180 to 230 ° C, and most preferably 190 to 220. (: range. If the molding temperature is too low, the molding will be unstable and it will easily fall into an excessive load. If the molding temperature is too high, the biological The extruded product obtained by decomposing the degradable polyester resin has problems such as reduced strength, coloration, etc. 314679 20. Extrusion molding can be used to make biodegradable sheets or pipes, but for the purpose of improving the heat resistance of these, Among biodegradable polyester resin compositions Heat treatment is performed at glass transition temperature (Tg) or higher and (Tm-20 ° C) or lower. Specific applications of biodegradable sheets or tubes manufactured by extrusion molding methods include raw material sheets for deep extrusion molding and batch foaming. Raw material sheets, credit cards and other cards, cushions, transparent clips, straws, hard tubes for agriculture and horticulture, etc. The biodegradable sheet can be deep-extruded by vacuum forming, pressure forming, and vacuum pressure forming. Manufacturing of food containers, agricultural and horticultural containers, foam-filled containers, pressure-filled containers, etc. The deep extrusion molding temperature and heat treatment temperature are preferably (Tg + 20 ° C) to (Tm-2 (TC)). Deep If the extrusion temperature is less than (Tg + 20 ° C), deep extrusion is difficult, and the heat resistance of the obtained container is insufficient. Relatively, if the extrusion temperature exceeds (Tm-20 ° C), uneven thickness will occur. Directional collapse, reducing impact. Food containers, agricultural and horticultural containers, foam-filled containers, and pressure-filled containers are not particularly limited in shape, but they are squeezed deep to the depth to accommodate food, articles, and medicines. 2mm It is better. The thickness of the container is not particularly limited. From a strength point of view, it is more preferably 50 0 // m or more, and more preferably 1 50 to 5 00 // m. Specific examples of food containers include fresh food. Food plates, instant food containers, fast food containers, bento boxes, etc. Specific examples of agricultural and horticultural containers include seedling pots. Specific examples of foam-filled containers include office supplies, toys, dry batteries, etc. Packaging containers for various product groups. Next, a blow molding method for manufacturing a blow molded product made from the biodegradable polyester resin composition 21 314679 of the present invention will be described. The blow molding method is a method of directly molding a raw material sheet. In the blow molding method, 1 injection molding is used for injection molding to prepare a preliminary product (bottomed prototype) after injection molding, and then to perform extension blow molding. x, can also be used to continuously blow the M-shaped slave-shaped method after the preparation of the product:

But take it out, and then heat it again for any of the cold release methods of blow molding ::; 2. The blow molding temperature should be (Tg + 2 (rc) to (Tm_2 (rc). If the blow molding temperature is less than (Tg + 20 ° c), the molding will be difficult, and the heat resistance of the obtained container will be insufficient.) If the plastic forming temperature exceeds (but m_20t > c), uneven thickness will occur, which will lead to problems such as leakage due to reduced viscosity.

The injection molding method for producing an injection product from the biodegradable polyester resin composition of the present invention may use a general injection molding method, and may also employ gas injection molding, injection pressure molding, and the like. The temperature of the barrel during injection molding must be above Tm or the flow start temperature, preferably 180 to 230 ° C, and more preferably 190 to 220 ° C. If the molding temperature is too low, a short circuit will occur, and it will become 7 without a son-in-law 'and Valley will easily fall into excessive load. On the other hand, if the molding temperature is too high, the biodegradable polyester resin will decompose, resulting in a reduction in the strength of the obtained product, such as coloring, etc. Problems are not good. In addition, the temperature of the mold must be below (Tm_2 (rc) ° in order to improve the heat resistance of the biodegradable polyester resin. When promoting crystallization in the mold, the temperature should be between (Tg + 20 ° C) to (Tm-20 ° C) ) It is better to cool to Tg or less after maintaining for a predetermined period of time. In contrast, when post-crystallization is performed, it is better to directly heat-treat the Tg to (Tm-2 (TC)) after the cold part is below Tg. In this case, the resin and foaming agent can be mixed in advance or 22 3] 4679 is formed by putting the foaming agent in the middle of the extruder. ^ ^ M molding. In this case, the general method can be applied 0 ′ through the above injection Restrictions on injection molding σ 4 manufactured by the molding method. Specific examples include plates, bowls, and: The second form does not have special permits such as tadpoles, knives, knives and other utensils, containers for liquids, cup molds for containers, and rulers. Shoji, finishing boxes, CD boxes and other office supplies, kitchen triangles, '5 deaths, washbasins, toothbrushes, combs, hangers and other wood, garbage, song > hanging supplies, flower pots, nursery plants · Gardening materials, plastic models, playing with temple soil, various toy boards, Refrigerator trays, various frames and other electrical systems, "Resin parts for clothes, anti-scratching, Hirakata 2: Resin parts for automotives such as decoration, etc." Also, liquid capacity "= No special restrictions ... accommodates liquids for molding For depth-the above is better. The thickness of the container is equal to 1, + Λ… special restrictions. From a strong point of view, Γ 1 ″ or higher is better, ο. 1 to 5 is better. Examples of limbs include dairy products, refreshing beverages, alcoholic beverages, cups and beverage jugs, soy sauce, tincture, menez, Fansu medicine, edible oil and other seasoning storage containers, shampoo, conditioner, etc. Containers, containers for chemical products, agricultural containers, etc. Examples Next, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples only. The following examples and comparative examples The measurement methods of various physical properties are as follows: (In the IV knife (1): using a gel permeation chromatography (Gel Permeatlng Chromamatrapby, Gpc) device equipped with a differential refractive index detector (Shimadzu Corporation) Made) to tetrahydro Furan was used as an eluent, and was obtained by converting polystyrene of standard 23 3J4679 at 40t. ⑺ Flexural modulus (Gpa): Based on the method disclosed in ASTM_790, 150 mm X 1 mm x 6 mm Read 4 test pieces of ρ ^ m and determine the flexural modulus of elasticity at a deformation speed of 1mm / min. (3) Melting point (C): using a differential scanning calorimeter Dsc_7 made by Jinwu Yasi). The temperature increase rate step / minute is measured, and the temperature at which the extreme value is given in the second search and desorption heat curve is taken as the melting point. (4) Melt Flow Rati (MFR) (g / 10): According to The method disclosed in jis K7210 is measured under the conditions of d in the eighth table of the description. (5) Tensile viscosity (1): A 60mmx 7mmx lmm (thickness) test piece was made using a tensile viscosity measuring device rme (manufactured by Raymettler), and both ends of the test piece were supported by a metal belt plate. When the melting point of the material is 10 ° C higher, the sample is rotated at a strain rate of 0.1 sec-], the tensile deformation is given to the measurement sample, and the tensile viscosity is sought by detecting the torque required to clamp the roller during the deformation. (6) Strain hardening coefficient (a2 / al): As shown in Figure 1, the inclination a in the initial linear area of the stretch is calculated until the inflection point appears on the two logarithmic plot of the stretch time and stretch viscosity. The ratio (a2 / a]) to the inclination a2 at the later stage of stretching after the zigzag point. In the measurement, a test piece of 7 mm x 60 mm < (thickness) was used. The melting temperature is the melting point of the resin + 丨 〇. (7) Crystallization speed index (minutes): Use a DSC device (Pyrisl DSC made by Barking Emma Co., Ltd.), as shown in Figure 2, to increase the fluidity from 20 ° C at a temperature increase rate of 5000t: / min. After rising to 200 ° C, the temperature was maintained at 20 ° C for 5 minutes. Then, the temperature was reduced from 200 ° C to 130 ° C at a temperature of 500 ° C / min at 314679 24, and then crystallized while maintaining the temperature at 130 ° C. When the final degree of crystallization is 丨, the time when the degree of crystallization reaches 0.5 is used as the obtained crystallization rate index (minutes). (8) Foaming ratio: Divide the mass of the foam by the foam The ratio of the foam density (D1) and the true resin density (D0) of the increased volume when immersed in water is calculated as an indicator of light weight and cushioning performance. Foaming ratio = D〇 / Di (9) Foaming Body appearance: 〇 · Uniform flaky surface with no roughness. X. Non-uniform flaky surface with rough surface due to bubble burst. (1 〇) Molding cycle (seconds). It is an indicator of injection moldability, using injection The molding device (manufactured by Toshiba Machine Co., IS_100E) releases the film at a molding temperature of 200 ° C and a mold temperature of 110 ° C. A cup model (38mm in diameter and 300mm in height) is subjected to injection molding, and the period of time until the cup mold can be well peeled off is inspected. (11) Blow molding: using a blow molding device (manufactured by Seiko ASB Corporation, ASB- 5〇HT), forming a model at a forming temperature of 20 (rc 30mm in diameter, = 100mm 'and 3.5mm thick. The obtained model was heated to a surface of 2 ° 80 ° C' in a bottle shape mold (90mm in diameter, high 25〇mm) ^ Plastic forming 'to produce a product with a thickness of 0.35mm. The appearance of the obtained product was evaluated in accordance with the following. 〇: Good products can be obtained according to the purpose △: Can be shaped approximately as the destination, but a part of it No X: Cannot be shaped as intended. 314679 25 (1 2) Dullness: The following operability was evaluated when manufacturing a biodegradable polyester resin composition. 〇 ·· Smooth operation for more than 1 hour X · Major problems such as wire breakage and propeller stoppage often occur. (13) Extrusion formability: The appearance of the product obtained by extrusion-molding the biodegradable polyester resin composition into a plate shape was evaluated as follows. 〇: None obtained Products with curved desired shape △ • Products Bending X: The product with the desired shape cannot be obtained. (14) Oxygen transmission coefficient (ml.mm/m2.dayMpa) ·· The resin pellets are press-formed into a sheet with a thickness of 300 // m using a differential pressure type. The gas transmission rate measuring device (manufactured by GTR Germany, GTR-3 × XAU) measures the oxygen transmission coefficient under the conditions of 20 c? C and 90% RH. The oxygen transmission coefficient is found by the following formula. The oxygen transmission coefficient m2_day. Mpa) = oxygen transmission volume (ml / m2.day, Mpa) x sheet thickness The oxygen transmission coefficient is the index of t-body barrier property. The smaller the value, the better the gas permeability. The raw materials and auxiliary materials used in the examples and comparative examples are shown below. (1) Biodegradable polyester resin: A: Polylactic acid (weight average molecular weight is 140,000, L-body is 99%, d-body is 1%, melting point is 168 ° C, MFR is ilg / 10 minutes) B: Polylactic acid (weight average molecular weight is 200,000, L body is 99%, 1% body is 1%, melting point is 168DC, MFR is 3g / 10 minutes) 314679 26 c: polylactic acid (weight average molecular weight is 150,000, L body is 96%, D body is 4%, melting point is 112 ° C, MFR is 10 g / 10 minutes. D: Polylactic acid resin (1, butanediol / succinic acid / lactic acid copolymer, Melting point: 110 ° C, MFR: 5g / 10min) E: Polybutylene succinate (melting point: 115 ° C, MFR: 30g / 10min) F: terephthalic acid / adipic acid / 1 , 4-butanediol copolymer, melting point is 108. 〇, MFR is 5g / 10 points) (2) (meth) acrylate compounds: I · ♦ Ethyl alcohol · Mono-methylpropionic acid S purpose (hereinafter not to be referred to as "PolyEthylene Glycol Dimethacrylate, PEGDM") (Manufactured by Nippon Oil & Fats Co., Ltd.) 曱 · Dimethylpropane bis-methylpropionic acid S purpose (hereinafter disclosed as "TriMethyl

Propane Tris Methacrylate, TMPTM ") (manufactured by Nippon Oil & Fats Co., Ltd.) Melon · Polyethylene glycol monopropionate (hereinafter disclosed as" Polly Ethylene Glycol Diacrylate, PEGDA ") (manufactured by Japan Fats & Oils Co., Ltd.) IV ·· Glycidol Glycyl acrylate (hereinafter referred to as "Giycidyl Methacrylate, GM") (manufactured by Japan Oil & Fat Co., Ltd.) (3) Layered silicate: ① Elastic S AN: Interlayer ion is via dimethyldi-octadecane Ammonium ion-replaced swelling montmorillonite (manufactured by Koff Chemical Co., Ltd., average particle size 〇 i β m) 〇 Elastic SEN: Interlayer ions are replaced by dihydroxyethylphosphonium dodecylammonium ion Swelling hectorite (manufactured by Koff Chemical Co., Ltd., average particle size 0 · 1 // m). ③ Jessian E: The interlayer ion is 314679 27 montmorillonite (made by Hexiu Co., Ltd., with an average particle size of 2 5 // m). ④Somaschiff MEE: The interlayer ion is a swelling fluoromica substituted by dihydroxyethylfluorenyldodecylammonium ion (manufactured by Kof Chemical Co., average particle size 6.3 // m). (4) Peroxides: ① Mono-peroxide tertiary butadiene (manufactured by Nippon Oil & Fats Co., Ltd.) ② 2,5-difluorenyl-2,5-bis (peroxide tertiary-butyl) hexyne_3 (Manufactured by Nippon Oil & Fats Co., Ltd.) ③ 2,5-Difluorenyl-2,5-bis (tertiary peroxybutyl) hexyne is an inert solid diluted powder (manufactured by Nippon Oil & Fats Co., Ltd.). Blended for use. Example 1 黾 3 A biodegradable polyester resin A: Polylactic acid (weight average molecular weight is 140,000, L body is 99%, D body is 1%, melting point is 168 ° C, MFR is 11§ / 10 points) 100 parts by mass, Y4 E4 parts by mass as a layered silicate, and 1.0 parts by mass of fine powdered talc powder (manufactured by Lim Kasei Co., Ltd., average particle diameter 2.5 # m), which was extruded with biaxial A kneader (PCM-30 manufactured by Ikegai Corporation, mold hole diameter 4 mmx 3H, kneading temperature 2000 ° C) was dry-blended and supplied to an extrusion feeder. Next, PEGDM, which is a (meth) acrylic acid compound I, is used in the ratio shown in Table 1. The PEGDM, the second peroxide in liquid form, the third-butane peroxide, and the acetic acid group as a plasticizer. Tributyl citrate was made into a mixture of 1 ·· 2 ·· 5 parts by mass and the solution was obtained. The obtained solution was supplied from the kneader through a liquid dosing pump. Melt and mix the above dry-blended resin and mixed solution

2S 3] 4679 Refined, extruded, processed into pellets and dried to obtain a biodegradable polyester resin composition. This biodegradable polystyrene resin composition and carbonic acid gas having a concentration of 1.0% by mass as a foaming agent were supplied to a biaxial extrusion foaming device (PCM-30 manufactured by Ikegai Corporation, die slit width: 1.2 mmx length 40mm), at a mixing temperature of 200 ° C and a molding temperature of 160. The physical properties of the resin composition and the foam obtained by making the foamed sheet 0 under the conditions of () are shown in Table 1. Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Biodegradable polymer Type of ester resin AAAAA 100 parts by mass 100 100 100 100 100 (fluorenyl) acrylic acid compound III.-I part by mass 0.1 1.0 3.0-12 layered silicate species ③ ③ ③ ③ ③ parts by mass 4 4 4 4 4 Fineness 〇〇〇〇χ MFR g / io points 1.3 0.8 0.6 11.8 Crystallization rate index points 2 1.5 0.5 32 — Strain hardening coefficient 14 18 25 1.03 _ oxygen transmission coefficient ml-mm / rri • day.MPa 140 152 ~ 140 155 Bending modulus GPa 3.8 4.1 4.3 3.0 Foaming ratio 5.1 8.0 10 (foam burst) — appearance of foam 〇〇J 〇X _ sheet size thickness X sheet width mmx mm 5x 42 7x 44 8x 48 lx 40 — In Examples 1 to 3, since the (fluorenyl) acrylate compound and the layered oxalate are blended within the scope of the present invention, the crystallization speed is fast and the operability is also good. Moreover, the strain hardening coefficient obtained is large, Flexural modulus Excellent biodegradable polyester resin composition. In addition, the layered polyester resin is mixed 3] 4679 29 Ishi & L salt, and the (fluorenyl) acrylate compound is melt-kneaded to obtain operation I4. Resin composition with excellent moldability. Foams using this biodegradable polyester resin composition have good foamability with independent foaming and uniform thickness. Compared with non-blended (fluorenyl) acrylate compounds, it is compared with Example 1 The same operation was performed to prepare a resin composition to obtain a foamed sheet. The physical properties of the obtained resin composition and foam are shown in Table i. Comparison 彳? ″ 丨 _2 · Except for (meth) acrylate compounds The blending ratio is other than 12 parts by mass of the scope of the present invention. The same operation as in Example i was performed to produce a foamed sheet. However, the resin composition could not be squeezed because it was too thick, and a sheet could not be obtained.

Since Comparative Example 1 did not contain a (meth) acrylic acid compound, it could not improve the mechanical strength of the wire with a bending elastic modulus, and it was a composition with a low strain hardening coefficient. Even if this resin composition is subjected to a foaming treatment, foam breakage occurs in combination, resulting in a foamed sheet having an uneven thickness. S Comparative Example 2 Since the compounding amount of the (meth) acrylic acid lysine compound is larger than the range of the present invention, it is too thick as described above, k θ is too thick, the resin composition cannot be stably pressed, and a resin composition cannot be produced. Examples 4 to 13 In addition to changing the types and blending ratios of the bio-based T-knife% polyester resin and (meth) propionate compounds in Example 1 as shown in Tables 2-1 and 2 Except for -2, the creep was performed in the same manner as in Example 1.焱 Biodegradable polyester resin group 314679 30 The obtained biodegradable polyester resin composition and carbon dioxide gas having a concentration of 1.0% by mass as a foaming agent were supplied to a biaxial extrusion foaming device (manufactured by Ikegai Corporation) PCM-45, die cut width: 0.7mm x length 65mm), foamed sheet was made under the conditions of mixing temperature of 200 ° C and mold temperature of 160 ° C. The physical properties of the obtained resin composition and foam are shown in Tables 2, 1, and 2-2. Table 2-1 Example 4 Example 5 Example 6 Example 7 Example 8 Mass fraction of biodegradable polyester AAABC resin 100 100 100 100 ^ ----- 100 (fluorenyl) acrylate type m I IV I ...... Bayi ------ I mass fraction of compound 0.10 0.10 0.10 0.10 IIglO ~ Type of layered silicate ③ ③ ③ ③ -------- ~ __________ 4 parts by mass 4 4 4 Operability 〇〇〇〜 ----- 〇MFR g / io points-1.2 1.3 0.9 --_ 1.1 Crystallization speed index points 2 2 1.5 4 ^ '-^ ------ ----- 20 Strain hardening coefficient 15 14 17 13 ——_ 12 Oxygen transmission coefficient ml * mm / nr • dayMPa 160 155 153 140 ^^, —____ ^^ __ 141 i Curvature GPa Γ 4.1 4.0 4.1 4.3 --- 4.0 Foam Magnification "7.5 7.3 7.6 7.2 ^ '7.0 Mann foam appearance appearance 〇〇〇 ------ 〇 sheet size thickness X sheet width mmx mm 5x 70 5x 68 6x 71 5x 67 .... J 5x 65-31 314679 Table 2-2 Example 9 Example 10 Example 11 Example 12 Example 13 Biodegradable polyester resin __ Type A / DA / EA / FA / EA / F 80/20 parts by mass 80/20 50/50 20/80 80/20 (fluorenyl) acrylic Type of ester compound IIIII 0.1 part 0.10 0.10 0.10 0.10 0.10 Layered silicate type ③ (3) ③ ③ ③ i part 4 4 4 4 4 operability 〇δ 〇〇〇〇FRFR / l0 points 1.1 0.8 0.6 0.9 0.8 Index of crystallization rate 3.2 3.6 4.0 3.2 5.5 Strain hardening coefficient 8 10 13 5.0 4.5 Oxygen transmission coefficient ml-mm / m2 • day-MPa 160 162 153 153 165 Flexural modulus GPa 3.9 3.7 3.3 3.6 3.7 Foaming magnification 7.0 7.5 8.1 5.2 4.3 Foam Appearance 0.0000 Sheet Size Thickness X Sheet Width Mmx mm 5x 66 7x 70 8x 70 4x 67 3x 67 Examples 4 to 6 are for changing the type of (fluorenyl) acrylate compounds, Examples 7 to 1 3 are those that change the type of biodegradable polyester resin. Since the ratio of the biodegradable polyester resin, layered silicate, and (fluorenyl) acrylate compound in any case is within the scope of the present invention Therefore, it is possible to obtain a foamed body with fast crystallization speed, large strain hardening coefficient, superior bending elasticity, and uniform independent foaming. Example 1 4 to 1 8 A biodegradable polyester resin composition was obtained in the same manner as in Example 1 except that the types and mixing ratios of the layered silicates are shown in Table 3-1. The obtained biodegradable polyester resin composition and a carbon dioxide gas having a temperature of 1.0% by mass as a foaming agent were supplied to a biaxial extrusion foaming device (PCM-45 manufactured by Ikegai Corporation, die cut Width: 0.7mmx length

" 1467Q 6 5mm), the properties of the resin composition and the foam obtained by switching to a foamed sheet under the conditions of a mixing temperature of 200 ° c and a mold temperature of 16 (TC) are shown in the table below. Decomposable PolyS Resin Ester Compound—Layered Stone

MFR crystallization rate index strain hardening coefficient flexural modulus foaming ratio foaming appearance appearance of sheet size thickness X sheet width kind mass parts kind mass parts kind mass parts g / i〇 cent points GPa ml-nun / m2 day.MPa mmx

Sub-Example I4 丨 Implementation Example 16 A AT A 100

I 0.10 ① 4 〇 0.5 2 1 · 8 4.0 170 5.6 〇 4χ 66 0.10

0.5 Ο.ί 2.5 4.0 172 6.0 〇4x 68 18 4.2 85 7.9 〇5x 70 10.2 120 〇5χ 72 22 4.5 60 ^ 〇 ~ 3) Γ67 ^ Examples 14 to 16 More layered linoleate seeds I member 17 And 18 are those that change the addition amount of the layered silicic acid layer. Because any one of the examples of the biodegradable poly-S resin, the layered fossilate and the (fluorenyl) acrylic acid eight compounds are all in the present The scope of the invention is Θ, the Q degree is fast, the strain hardening coefficient is also large, the curvature elasticity is excellent, and the foam is 2 to 2-. X, as shown in Example 16, the use of Somaschiff's as a layered stone Xixi salt 'can improve gas collision resistance in particular. As shown in Examples% 16 33 to 18 liters. The more the layered silicate is added, the more the gas barrier property is improved.

Except that you use Somaschiff MEE as the layered silicate, and its mixing ratio ^ is 0.03 parts by mass of the range of the present invention, the same operation as in Example 1 is used to make a resin composition to obtain foaming. Flakes. The physical properties of the obtained resin composition and foam are shown in Table 3.

Except that Somaschiff MEE was used as the layered silicate, and its blending ratio was 22 parts by mass more than the scope of the present invention, the same operation was performed as in the example] to make a foamed sheet, but because the viscosity was too low, The resin composition cannot be pressed, and a sheet cannot be obtained. In Comparative Example 3, since the content of the layered silicate is too small, the oxygen transmission coefficient becomes large, the strain hardening coefficient decreases, and the mechanical strength cannot be improved. In Comparative Example 4, since the content of the layered oxalate was too large, sufficient thickening property could not be obtained, and the gas barrier property was lowered. In addition, as described above, foam breakage occurs, and a foamed sheet having a uniform thickness cannot be obtained. 314679 34 Table 3-2

_ Except for the biodegradable polyester resin A: polylactic acid (weight: molecular weight of 140,000, L body is ... body is ⑼, melting point Π 6 C, running is llg / 10 points) ⑽ mass parts, as Lamellar acid ^ Μ 4 mass parts of Mashev bile and average grains used as a core agent: Micronized powder talc powder (manufactured by Japan Talc) 15 f wide amount plus the addition of K0 mass% for the resin component An oxidizing knife, and a base di-bis (third-butyl peroxide) hexadecane-3 dilute dimethionate, was added in Example 1.轴 ㈣㈣ # is fed to the squeeze feeder. Next, it was made as < Tun blending, and supplied with PEGDM 0.1 parts by mass and Λ 'A @enoate compound as a plasticizer, and ethyl tributyl 35, which was intended to be 1: 5 parts by mass. The mixed solution in a proportion is supplied from the middle of the kneader by a liquid dosing pump. The dry-blended resin and the mixed solution are melt-kneaded, extruded, processed into pellets, and dried to obtain a biodegradable polyester resin composition. The obtained biodegradable polyester resin composition was put into a separate bubble device (manufactured by Pressure Resistant Glass Industry Co., Ltd., 500ml), and the temperature was set at 150 ° C, the carbon dioxide gas injection pressure was i5MPa, and the carbon dioxide gas injection time After 60 minutes, the pressure was released in one breath to produce a carbonic acid gas batch foam. The physical properties of the obtained resin composition and foam are shown in Table 4. Table 4 Example 1 9 Example 20 Type of biodegradable polyester resin AA 100 parts by mass 100 100 (fluorenyl) acrylic acid g Compound type II 0.1 parts by mass 0.10 0.1〇 Layered silicate species—④ _ mass parts 4 4 operability 〇〇FRFR g / io points 0.9 0.9 crystallization rate index points 0.5 0.5 strain hardening coefficient __18 18 flexural modulus GPa 4.2 4.2 expansion ratio 34 54 appearance of the foam 〇 Example 20 Except for D :) : A batch foam was produced in the same manner as in Example 19 except that the carbon dioxide gas was used as the blowing agent instead of the carbon dioxide gas. The physical properties of the obtained resin composition and foam are shown in Table 4. In Example 19, the thickening effect due to the (fluorenyl) acrylate compound was improved. 36 314679, so that a foaming body having a high crystallization speed, a large strain hardening coefficient, and an independent cell shape was obtained as a high magnification. In Example 20, a butane gas was used as a foaming agent, and the resin had a high solubility in the foaming agent, and a foam having a high independent unit cell% with a higher expansion ratio was obtained. 1 fox and 1 night 丨 J 2 1 The biaxial mixing type foaming and thinning device (made by Toshiba Machine Co., Ltd., TEM48BS type) for the biodegradable polymer resin composition obtained in the example, the die cut interval: 〇 3 positions, periodical die ejection and .160 ° surface smelting and smelting at a temperature of 210 ° C, in the cooling zone; :: degree is given, die temperature is 160t, and carbon dioxide gas concentration is 20% of soil output : Under the condition of 50Kg / h, the sheet was made through a sheet width of 64〇_x2 removal methods at a removal speed of 15m / min. The result: The obtained foamed sheet was made by a thickness of 2〇_, and was sent separately 4-21 Foamed sheet composed of cells. X, bending elasticity rate is 4GPa, which is a sheet with excellent mechanical strength. The foamed sheet is formed by a constant temperature machine (a shallow mold made from a cup mold and a container-body mold. Nine pounds = clothing Manufacture) Warp ratio (㈣⑴). Specifically ^ ... Use a plate (container squeezing room to move on the mold after 10 seconds, degree: 4 I30C, vacuum forming for 5 seconds when heating, to obtain the product. ⑨ 吴 有 温度】] The product has no forming defects on the plate. The foaming ratio of the plate is uniform-hair The state of the food sheet is the same. The foaming ratio is the same as that before molding. 314679 37 Bu Fang ... Hei Menzi's main water into the water, the microwave oven (output 500W) for 3 minutes. The result is the processed plate There is almost no shrinkage. Example 2 2, 2 3 Ex. Example 22 uses the biodegradable polymer resin composition obtained in Example 2, and Example 23 uses the biodegradable polymer obtained in Example 19. The resin composition was injection-molded in an injection molding apparatus (manufactured by Toshiba Machinery Co., Ltd., IS-100E) in a mold-removal cup model (38 mm in diameter and 300 mm in height). The molding temperature was 200 ° C, and the mold temperature was U (at rc). Check the cycle time until the cup mold can be released. The obtained measurement results are shown in Table 5. Table 5 Example 22 Example 23 Comparative Example 5 Comparative Example 6 Comparative Example 7 ϋ Degradable polyester resin type AAAAA quality 1 part 100 100 100 ~ 00 ~ 100 (meth) acrylic acid compound type II — I 1 part by mass Γ 1.0 0.10-0.10 Layered crushed acid salt type r③ r③ ④ I part by mass. 4 4 4 0.03 One operability 〇〇 〇〇MFR g / ΐο points 1 .3 0.9 11.8 1.4 11 — index of crystallization rate 2 0.5 32 0.2 110 strain hardening coefficient 14 18 1.03 0.4-forming cycle seconds 45 40 120 55 600 above Examples 22 and 23, due to the layered silicate and (曱Multiplication effect of acrylic compounds, the crystallization speed becomes faster, and the molding cycle time becomes shorter. Comparative Examples 5 and 6 Except for the use of the biodegradable polymer resin composition obtained in Comparative Example 1 in Comparative Example 5, and the use of the biodegradable resin composition obtained in Comparative Example 3 in Comparative Example 314 679 38 polyacetate resin composition 'and Examples 22 In the same operation, perform the injection molding 'check the cycle time until the cup mold can be released. The obtained measurement results are shown in Table 5. Comparative Example 7 Except that the (fluorenyl) acrylic compound and layered oxalate were not blended, and only the biodegradable polymer used in Example 1 was used, the same operation as in Example 22 was performed when injection molding was performed, due to poor operability. Cannot be implemented. In Comparative Example 5, since the (fluorenyl) acrylic compound was not blended, the crystallization rate was very slow, and the molding cycle was significantly reduced. Side; Comparative Example 6, because the proportion of the layered silicate is too small, the thermal rigidity is insufficient, 'difficult when taking out the product', and the operability during injection molding is poor: In Comparative Example 7, due to the lack of (meth) acrylic compound and The layered fossilate does not exhibit strain hardening and has a slow crystallization rate, and it is almost impossible to perform the operation as described above. Examples 24 and 25 In the yoke example 24, the biodegradable polyester resin composition obtained in Example 2 was used, and in Example 25, the biodegradable polyester resin composition obtained in Example 19 was used in blow molding. Forming device (manufactured by Nissei Asb, ASB-50HT). Under the condition of forming temperature 2000t, a pre-model with a diameter of 30 mm, a height of 100 mm and a thickness of 3 5 mm is heated, and the obtained pre-blade type is heated to a surface temperature of After that, blow molding was performed in a bottle-shaped mold (90 mm in diameter, 250 mm in diameter) to obtain a product having a thickness of 35 μm. The measurement results obtained are shown in Table 6. Table 6

Example 24 Example 25 Comparative Example 8 Comparative Example 9 Comparative Example 10 Type of biodegradable polyacetate resin AAAAA 100 parts by mass 100 100 100 100 100 (fluorenyl) acrylic acid compound type II-I-part by mass 1.0 0.10-0.10- Types of layered silicates ③ ④ ③ ④ One part by mass 4 "4 4" 0.03 One operability 0.0000 MFR g / ΐο points 1.3 0.9 11.8 1.4 11 crystallization rate index points 2 0.5 32 0.2 110 strain hardening coefficient 14 18 1.03 0.4 — Blow moldability 〇〇 △ ΔX In Examples 24 and 25, due to the multiplication effect of the layered silicate and the (fluorenyl) acrylic acid compound, the crystallization speed becomes faster and the blow molding The moldability is good. Comparing with the examples 8 and 9 except that Comparative Example 8 is a composition using the biodegradable polyester resin obtained in Comparative Example 1, and Comparative Example 9 is a composition using the biodegradable polyester resin obtained in Comparative Example 3. Except for the other materials, blow molding was performed in the same manner as in Example 24. The measured results are shown in Table 5. Comparative Example 1 Except for the non-blended (fluorenyl) acrylic compound and layered silicate, Except that only the biodegradable polyester used in Example 1 was used, the same operation as in Example 24 was used to perform blow molding. Because of its poor operability, the & method was used. Base) acrylic compounds, so only products with high MFR and slow crystallization can be obtained with poor blow moldability. Also, the obtained products are not suitable. For Comparative Example 9, from% ># _ Tian Wan 3. The proportion of layered silicate is too small, the thermal stability is insufficient, and it is difficult to take out the product, and the operability is poor. Part of the obtained product is not suitable. In Comparative Example 10, because the (meth) acrylic compound and layer were not compounded As a lithostrate salt, it does not exhibit strain hardening, and the crystallization speed is also slow. It is almost impossible to perform blow molding as described above, and the intended product cannot be obtained. Example 2 6 and 9 7 Example 26 is an example of use 2 The obtained biodegradable polyester resin composition, Example 27 is a biodegradable polyester resin composition 'obtained in Example 19 on a press molding machine (p C μ _ 3〇, manufactured by Ikegai Corporation) Molding temperature is under 2i (rC conditions of production 5〇mm width, a thickness of 2 〇mm forming plate. The measurement results obtained are shown in Table 7 below. TABLE 7

Example 26 Example 27 Comparative Example 11 Comparative Example 12 Comparative Example 13 Type of biodegradable polyester resin AAAAA 100 parts by mass 100 100 100 100 100 (fluorenyl) acrylate compound type II-I-1 part by mass 1.0 0.10 — 0.10 — layer Kinds of silicate ③ ④ ③ ④ One part by mass 4 4 4 0.03 ——Operability 〇1 〇 ~~ δ ~~ | 〇_ MFR g / io points 1.3 0.9 11.8 1.4 11 Crystallization rate index points 2 0.5 32 0.2 110 strain hardening coefficient 14 18 1.03 0.4-Extrusion formability 〇ΔΔΔX In Examples 26 and 27, due to the multiplicative effect of the layered silicate and the (fluorenyl) acrylic compound, the crystallization speed is fast. Good press formability. Comparative Examples 11, 12 Except for Comparative Example 11, the biodegradability obtained using Comparative Example 1

41 ^ 1467Q Polyester resin composition, Comparative Example 12 was extrusion-molded in the same manner as in Example 26 except that the biodegradable polyester resin composition obtained in Comparative Example 3 was used. The measurement results obtained are shown in Table 7. Comparative Example 1 3 Extrusion was carried out in the same manner as in Example 26 except that the (fluorenyl) acrylic acid compound and layered oxalate were not used, and only the biodegradable polyester used in Example 1 was used. However, it cannot be implemented due to poor operability. In Comparative Example 11, since the (meth) acrylic compound was not blended, the MFR was south, the crystallization rate was slow, the board was bent, and the extrusion formability was poor. In Comparative Example 12, since the proportion of the layered silicate was too small, the thermal rigidity was insufficient, and the board was bent, so that a product having a desired shape could not be obtained. In Comparative Example 13, since (meth) acrylic compound and layered silicate were not blended, strain hardening was not exhibited, and the crystallization rate was also slow. Extrusion molding as described above was almost impossible, and the intended product could not be obtained. . [Simplified description of the drawing] Fig. 1 is a graph showing the relationship between the elongation time used to obtain the strain hardening coefficient (a2 / a) and the elongation of the person [pa s]. a] is the inclination of the linear area at the initial stage of stretching until the inflection point M appears, ^ is a] and the inclination of the late stage of stretching after the inflection point. Fig. 2 is a graph showing the relationship between the degree of crystallization (?) And time (minutes) to obtain the crystallization rate index. The crystallization rate index is the time (minutes) until the final crystallization degree reaches 1/2. 314679 42

Claims (1)

Scope of patent application: 1. A biodegradable polyester resin composition, characterized in that it contains 100 parts by mass of a biooctalytic polyester resin containing 50 mol% or more of hydroxycarboxylic acid units, (fluorenyl) acrylate Compound OIf to 10 parts by mass and layered silicate 0.05 to 20 parts by mass. 2. The biodegradable polyester resin composition according to item 1 of the scope of patent application, wherein the crystallization rate index is 30 (minutes) or less. 3. If the biodegradable polyfluorene resin composition of item (i) or (ii) of the scope of patent application, the (fluorenyl) acrylate compound has two or more (fluorenyl) acryl groups or more than one in the molecule. A VTI) acryl and one or more glycidyl or vinyl. (For example, a biological polyester resin composition in any one of items i to 3 of the scope of application for a patent, in which and / or the hydroxycarboxylic acid unit is D-lactic acid, L-lactic acid, or a mixture thereof. 5 For example, the scope of the patent application Nos. 1 to 4 Noni K < biodegradable polyacetate resin composition, wherein the melting point is higher than the melting point of the biodegradable polyacetate tree dagger composition by 1 (rc temperature measurement When the degree of stretching is obtained ^ In the tensile viscosity curve, the inclination a of the initial stage of stretching until the inflection point appears, [a] and the inclination / ratio of the inflection stage after the inflection point (strain hardening coefficient = a2) / a] _ le05 or more and more than 50%. 6 · —A method for manufacturing a biodegradable polymer resin composition of any one of T in the scope of application for patents 1 to 5 "Convergence is: after mixing the biodegradable polyester resin composition with the layered silicic acid step sol, and then mixing it with (fluorenyl) acrylic acid SI compound and peroxide ~ 7 grains. Ή V70 43 7 · Any one of the items i to 5 in the scope of application for patents—Biodiversity ~ Polyester The method for producing a fat composition is characterized in that the biodegradable polyester resin composition is melt-kneaded with a layered silicate, and then a solution or dispersion of a (meth) acrylate compound is injected and melted. 8 · —A method for producing a biodegradable polyester resin composition according to any one of claims 丨 to 5 of the scope of patent application, characterized in that the biodegradable polyester resin composition and the layer are ... After melt-kneading the silicate-like silicate, a solution or dispersion of (meth) acrylic acid ester compound and peroxide is injected and melt-kneaded. 9. A biodegradable resin foam characterized by: The biodegradable polyester resin composition according to any one of the scope of application patents Nos. 1 to 5 is formed by foam molding. 1 0-A kind of biodegradable polyester resin products, characterized in that: The biodegradable polymer resin composition according to any one of the scope of patents Nos. 1 to 5 is formed by any one of injection molding, injection molding, and blow molding. 314679 44