TW201221579A - Polylatic acid and polyolefin-based composition - Google Patents

Abstract

The present invention relates to a composition of poly lactic acid and poly allyl series, characterized in that the total amount is 100 wt %, and 4.5 to 30 wt % of poly lactic acid resin, 25 to 93.0 wt % of poly allyl resin and 2.5 to 45 wt % of a modified poly allyl compound; and the content of the modified poly allyl compound is 0.25-fold higher and 1.5-fold less than that of the poly lactic acid resin.

Description

201221579 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a polylactic acid and a polyalkenyl-based composition which are used especially in the production of a plastic article such as a film. [Prior Art] [00〇2] In recent years, a large number of various plastic products have been used in daily life. As a result, from the viewpoint of natural environmental protection, problems such as handling after use of the plastic products are generated. For example, packaging trays, shopping bags, draining nets, and seedling pots used in supermarkets and the like are formed by extrusion molding. These disposable plastic materials are used daily as garbage and emit large quantities from household or commercial facilities. In the current situation, most of these are discarded by incineration. However, most of these use general-purpose plastics from petrochemical resources, which mainly use polyalkenyl-based resins. Since the past, these plastic materials have a high calorie burning degree, which has a problem of injuring the incinerator. At the same time, recently, when these materials are completely incinerated, the carbon in the two substances will act as c〇2, and the breath will be released, thus posing as the main cause of geothermalization. The means to solve this problem, in the past decade or so, the use of tens of% of carbonic acid mobile phones 'added to the polyalkenyl resin to reduce the calorific value = ° However, the added inorganic residue as a gray, but instead Being associated is considered a problem. In terms of the production of CO, it is still in an unresolved situation. The countermeasures are required to reduce the amount of heat generated during combustion, and as a material that does not leave a large amount of residue. Among them, the material is proposed 10014014# single number _, base (four) is a forming composition, which contains: modified by unsaturated taurine or UU14Ui page 3 / 23 pages 1013041242-0 201221579 A dilute base resin, a mixture of a polyalkenyl resin modified with an unsaturated tarenic acid or a derivative thereof, an unmodified polyalkenyl resin, and a starch-based material (Patent Document 1). The polyalkenyl-starch-forming composition is characterized by good workability, thermal fluidity, and photodegradability, and has practically sufficient mechanical strength. In addition, a polylactic acid-modified polyalkenyl resin composition is proposed in addition to the polyalkenyl-starch molding composition, and the polylactic acid resin is modified by an unsaturated carboxylic acid or a derivative thereof. Polyalkenyl resin (Patent Documents 2 and 3). These polylactic acid-modified polyalkenyl resin compositions are characterized by good strength and impact resistance and biodegradability. However, when the polyalkenyl-starch-based composition as described above is used for general film use, since the composition contains a temple powder system, when it is disposed of as garbage and incinerated, the calories during burning are lowered. Solve the problem of ash residue, but it has the following problems. (1) Due to the influence of the starch system in the composition, the main cause of "odor" and "gas generation" during molding is to pay attention to the temperature control during molding. (2) Due to the influence of the starch system in the composition, even if the temperature control at the time of molding is taken care of, the starch composition is still affected by the heat during molding, and discoloration is caused, and a transparent film cannot be obtained. (3) Suitable as a recycling bag for garbage generated by household or commercial facilities. However, since the composition contains a starch-based composition, it is not suitable for a plastic film which is directly in contact with the mouth. In order to solve the problem, the applicant of the present invention has proposed a molded article of a polylactic acid and a polyalkenyl-based composition in which polyacrylic acid is added in an amount of 10% to a polyalkenyl resin (Patent Document 4). According to the molded article of the polylactic acid and the polyalkenyl-based composition of Patent Document 4, it can be formed with a resin of the conventional polyalkenyl group, a single-numbered A0101, a fourth page, a total of 23 pages, 1010306142-0, 201221579 resin. The product has the same mechanical properties and quality characteristics, and it can also suppress the amount of 〇2 produced during disposal. This type of polylactic acid and polyalkenyl-based compounds have a high polylactic acid content and can be completely decomposed in the natural environment. Therefore, when it is disposed of as waste after use, it can be advantageously disposed of by landfill with conventional incineration waste. However, it has the following problems. (4) The resin component is polylactic acid and modified polyalkenyl. The price of each resin is as high as 2. 5 to 10 times the price of the alkenyl resin. Therefore, although it is effective from the viewpoint of disposal, the cost of the product price increases. (5) At the time of forming, it is necessary to For the time being, the respective resins are mixed and stirred by a twin-screw extrusion mixer, and are melt-extruded and subjected to exfoliation and granulation as a main raw material, thereby implying a further increase in the cost of the main raw material. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-316310 (Patent Document 2) [Patent Document 4] Japanese Patent Laid-Open Publication No. 20 07-30 8638 [Description of the Invention] [0003] It is an object of the present invention to provide a low-cost polylactic acid and polyalkenyl-based composition which overcomes polyalkenyl groups and The above problems (1) to (3) in the case of molding the starch-based composition, and the above problems (4) and (5) in the formation of the polylactic acid and the modified polyalkenyl resin composition, the polylactic acid is used. It is characterized by rigidity, good impact resistance, and good formability and high mechanical strength. 1001401#Item No.1 Page 5 of 231013006142-0 201221579 Polylactic acid and polyalkenyl composition of the present invention 5〜45质量百分比; The above modification is as follows: the total amount is 10D% by mass, and the polylactic acid resin is contained in an amount of 5. 5~30% by mass, polyalkenyl resin 25~93. 0% by mass and modified polybasic compound 2. 5~45% by mass; The polyalkenyl compound is contained in an amount of more than 25 times the amount of the polylactic acid resin. According to the present invention, it is possible to obtain a low-cost polylactic acid and a poly-based base composition which are characterized by the use of polylactic acid, that is, rigidity, and excellent in impact resistance, and having moldability and high mechanical strength. Embodiments [0004] Hereinafter, the present invention will be described in further detail. In the present invention, the polylactic acid resin is a resin which is lactic acidated and polymerized by a plant powder of corn, potato, sweet potato, etc., which means only from lactic acid, D - a polymer composed of a monomer unit of lactic acid, L-lactic acid, and D-lactic acid. By producing a resin obtained by lactic acidating and polymerizing a polylactic acid resin, the amount of c〇2 can be suppressed.丨5~1〇% ratio. The polylactic acid resin can be produced by any conventional polymerization method. The most representative method is to transfer the lactic acid to the lactic acid, and to carry out the ring-opening polymerization method (lactic acid vinegar method), but it is also possible to directly condense the lactic acid. The polylactic acid resin is composed of a monomer unit derived from an L-lactic acid resin or a D-lactic acid resin, or a lactic acid resin and a D-milk lysate, and the polymer is crystalline and has a high melting point. Further, by changing the ratio of the monomer unit derived from the L-lactic acid resin and the D-lactic acid resin (hereinafter referred to as l/d), the crystallinity and melting point can be freely adjusted. Such polylactic acid resin commercials are, for example, manufactured by Mitsui Chemicals Co., Ltd., trade names: LACEA and Nature.

Works ; 10014014 Lu single number A0101 Toyota Motor Co., Ltd., trade name: Ec〇 Page 6 of 23 1013006142-0 201221579

Plastics u' z; and Zhejiang Haisheng Biomaterials Co., Ltd., trade name: REV00E; in the present invention, any resin can be used 〇

The amount of the polylactic acid resin added is 4.5 to 30% by mass, but more preferably 10 to 20% by mass, because of good mechanical properties during use, and is advantageous for the CO 2 reduction effect. When the amount of the polylactic acid resin added is less than 4.5% by mass, the amount of the olefinic resin is large, so that the effect of sufficiently maintaining the mechanical properties and having a high oxygen permeability can be obtained. However, it was not possible to impart microbial disintegration ‘ and the calorie-reducing effect was not confirmed. Moreover, the c〇2 reduction effect is also less than 1.0%, so it is not suitable. Further, when the added stem of the polylactic acid resin exceeds 30% by mass, it is advantageous for microbial disintegration, but a hard and brittle film is obtained, resulting in a decrease in oxygen permeability. Further, since the texture of the film is hard, wrinkles and the like are formed during molding, and there is a problem that the molding cannot be stably formed. In the present invention, various materials can be used as the polyalkenyl resin, and suitable are, for example, polypropylene, high density polyethylene (hereinafter referred to as HDPE), medium density polyethylene (hereinafter referred to as LLDPE), and low density polyethylene (hereinafter referred to as a single-dilute polymer such as LDpE), poly-4-mercapto pentylene or the like, or a propylene-propylene copolymer 4, an ethylene-gasified vinyl copolymer, a propylene-gasified vinyl copolymer or the like a mixture of polymers. The polyalkenyl resin is added in an amount of 25 to 93 % by mass, but more preferably 50 to 75% by mass, because it can utilize the characteristics of polylactic acid, and is beneficial to (3) the effect of reduction and the reduction of calories burned. When the amount of the addition of the lipid is less than 25% by mass, the characteristic of the polylactic acid is strong, and the effect of removing the soil is significantly increased. The effect of biodegradability/disintegration 2 or a film having good transparency can be obtained. "Because of the strong influence of the characteristics of polylactic acid, the film of hard 跪 is obtained, in the impact resistance test, at 1〇10014014#单号A〇101 Page 7 / 23 pages 1013041242-0 201221579 times In other words, when the amount of the polyalkenyl resin added exceeds 93.0% by mass, the hot air strength also shows a very high value due to the influence of many polyalkenyl resins. Impact resistance {•生和和;, even if it is given more than 3 times of impact, it is still difficult to cause the bottom to fall off or the body to crack, and the film with good mechanical properties can be obtained. However, the calorific effect of burning calories cannot be obtained. The alkenyl resin is not limited to one type, and two or more types of polyethylene resins can be used in combination, for example, a polyethylene resin such as a polyalkenyl resin. The types of the polyethylene resin are classified into HDPE, LLDPE, and LDPE. JIS specification: K6922-U plastic polyethylene (pe) forming and extrusion materials) is classified into three types of 16 types of specific gravity according to quality items such as density and melting ratio. 942 or more is classified as HDPE, and specific gravity is 〇. LDE is classified as upper and lower than 93. LLDpE is a synthetic resin known as a thermoplastic resin obtained by copolymerizing ethylene with a certain amount of a-alkenyl group, and is defined as a density of more than 91 〇 and less than 〇. 925 in JIS K6899-1:2000. Linear polyethylene copolymer LLDP is a resin of the name linear low-density polyethylene. Moreover, the resistance of LLDP is ', ', and high (about 125. (:)' is equivalent to HDPE and LDPE. In the middle of the resin, the garbage bags that are often used in the home are formed by HDPE and LLDP. The shopping bags used in supermarkets and the like are based on HDPE. However, if there is no problem in terms of forming or mechanical properties,倍倍。 The polyethylene resin is preferably a polyethylene resin, the polyethylene resin is preferably 0.10 times the polylactic acid resin. The above, 20. 7 times or less. Here, > *, such as l〇〇l4〇u dream list number A_1 right polyethylene resin is less than 0.11 times, the amount of polyalkenyl resin added 101016014-2-0 page 8 / A total of 23 pages 201221579 will increase 'resin mutual compatibility The improvement is improved, but the cost is increased because the addition amount of the modified poly-base is increased. Further, if it exceeds 2〇7 times, the addition amount of the polyethylene resin becomes larger, and the addition amount of the poly-based resin becomes less, so the resins are mutually added. The compatibility is deteriorated, and unevenness is generated on the surface of the film, and a uniform film cannot be obtained. In the present invention, it is preferable to add LL of 5 to 15 parts by mass with respect to the mass portion of the polyethylene resin. In this case, LLDp can obtain a good compatibility of the composition of the metal of the rhyme, and the mechanical properties are also good. Here, when the LLDPE is less than 5 parts by mass, the characteristics of the main matrix (HDPE) become strong, and the tensile strength or impact strength is good, but p, which can obtain a film close to Qian Ming, and LLDP exceeds 15 mass parts, and is lost. _ Ε characteristics. Therefore, it is preferable to add LLDP at a ratio suitable for mechanical properties and use. Further, the metallocene polyethylene refers to a polymer which is polymerized by a metallocene catalyst (Kaminsky catalyst), which is one of LLDPE. Here, the metallocene catalyst system group. - Gasification and methylation, which have a high degree of polymerization activity for ethylene and an average of active sites. Compared with the composition of the so-called ffDPE or LDPE and LLDPE, the cost is high. If the amount of addition is increased, the cost is high. (4) The quality of the main matrix (component with high composition ratio) is deleted. Department, should be 5 to 15 quality departments. In the present invention, the copolymer of the following (1) to (6) is exemplified as the modified polybasic compound. (1) A copolymer obtained by graft-polymerizing (meth)acrylic acid vinegar or stupid ethylene copolymer with a copolymer of dilute base and acrylic acid vinegar. (1) Copolymer of α-thinyl group and vinyl acetate a copolymer obtained by grafting or polymerizing a vinyl acrylate or a stupid ethylene. Brain side dream single Wei 1013001412-0 201221579 (3) α-dilute group and glycidyl group containing ethylenic unsaturated bond a copolymer of a monomer. (4) A copolymer obtained by graft-polymerizing a dilute base with ethylene and an acrylate and an acid anhydride. (5) A copolymer of α-alkenyl and ethylene-propylene to which maleic acid is attached A copolymer obtained by polymerizing a branch. (6) A copolymer obtained by graft-polymerizing an ethylene-based copolymer unsaturated carboxylic acid or a derivative thereof composed of an α-alkenyl group other than ethylene. The alkenyl group may, for example, be ethylene, propylene, dibutyl-1, dilute-1, 4-methylbutene-1 or 4-mercaptobutene-1, but is preferably ethylene or propylene. The glycidyl group-containing monomer to which the unsaturated group is bonded may, for example, be diglycidyl acrylate, methacrylic acid diglycidyl group or itaconic acid monocondensed water. Oil ester, butylene tricarboxylic acid diglycidyl ester, butylene tricarboxylic acid monoglycidyl ester, butylene tricarboxylic acid triglycidyl ester, etc., or glycidyl glycidyl S, propylene A glycidyl vinegar or a glycidyl ethoxy ether. The (meth) acrylate may, for example, be a methyl acrylate, an ethyl methacrylate, an ethyl acrylate or an ethyl methacrylate, but as an impact modifier. In particular, the methacrylic acid methacrylate group is preferably the following (1) to (7). (1) (ethylene + maleic anhydride) graft copolymer (trade name: ADMER, Mitsui) (2) Alpha-alkenyl-propylene copolymer (trade name: TAFUMER, manufactured by Mitsui Chemicals, Inc.) (3) Ethylene-glycidyl methacrylate copolymer grafted oxime (commodity) Name: M0DIPER Α4200, manufactured by Nippon Oil & Fat Co., Ltd.) 1001401#^ Α〇101 Page 10 of 231013006142-0 201221579 (4) Ethylene-ethyl acrylate copolymer grafted pMMA (trade name: MODIPER A5200 Japan Oil and Fat Co., Ltd. (5) Ethylene-vinyl acetate copolymer grafted PMMA (trade name: MODIPER A6200, manufactured by Nippon Oil & Fat Co., Ltd.) (6) Ethylene-ethyl acrylate-maleic anhydride copolymerized pMMA (commodity) Name: MODIPER A8200, manufactured by Nippon Oil & Fat Co., Ltd.) (7) Ethylene-glycidyl methacrylate (E_GMA) copolymer and terpolymer (trade name: B0NDFAST, Sumitomo Chemical Co., Ltd.) The addition of the polyalkenyl compound is from 2 to 5 to 45% by mass, but it is preferably from 5 to 20% by mass from the viewpoint of unevenness of the resin on the surface of the knee membrane or benefit from glossiness. Here, when the addition amount of the modified poly-based compound is less than 2.5% by volume, 'the physical property improvement and the compatibility effect by the addition are not confirmed.>> The addition amount of the "Tian modified poly-based compound" When it exceeds 45 mass%, the compatibility effect of a polylactic acid resin and a poly-base resin can be confirmed. However, 〇 * body. The content of the poly-dense-based compound is increased, and the effect of using the organism as a raw material of the energy m cannot be exhibited. Further, the ratio of the raw material of the modified poly-based compound is 2.5 times or more as compared with the poly-based resin. Therefore, if the addition ratio of the modified poly-based compound is added, the cost of the molded product occurs. Raised question. The present invention has a polymorphic compound which is more than 0. 25 times and less than 1 q pull. D times. Here, if the modified polyalkenyl compound is small; when the compound is used to produce a plastic molded article such as a film, the pepper is not uniformly formed on the surface of the film, and partial peeling is observed in the film. No problems such as glossiness were observed on the surface. In other words, 1001401# single number A0101 page 11 / total 23 w ' ^ 1013006142-0 201221579 C〇2 cut-off rate (%) is 0.25 times or less, can not meet the c〇2 cut-off rate found in the present invention (%). Further, when the modified polyalkenyl compound was 1.5 times or more with respect to the polylactic acid resin, no resin unevenness was observed on the surface of the film, and it was suitable from the viewpoint of compatibility, but wrinkles were partially formed. In the present invention, although it is not particularly limited, if there is a problem such as opening property or smoothness of the base film during molding, it may be added as needed to add a plasticizer. The plasticizer is considered from the viewpoint of the overall compatibility and plasticizing ability for polylactic acid or a modified polyalkenyl compound, and is preferably selected from an aliphatic dibasic acid ester system, a phthalic acid ester system, and a phthalic acid ester. An acid ester type, a hydroxy polyvalent carboxylic acid ester type, a glycolic acid derivative, an ether ester derivative, a cellulose derivative, an alkyl phosphate type, a dialkyl ester type, a diester type, a tricarboxylic acid ester type, Polyester, epoxy, sulfonium sulfonate, ether ester, benzoate, polyglycol diacetate, alkyl ketone, fatty acid vinegar, alkyl ketone At least one or more of the group consisting of ester plasticizers is composed. In the present invention, a pigment, an oxidation preventive agent, a plasticizer, a charge preventive agent, a delustering agent, a deterioration preventive agent, a fluorescent whitening agent, an ultraviolet absorber, an ultraviolet stabilizer, a slip agent may be added at an arbitrary ratio as needed. , crystal nucleating agent, metal powder, inorganic filler, carbon black, tackifier, clay stabilizer, etc. The polylactic acid and the polyalkenyl-based composition of the present invention can be obtained by a general air film forming method, an air blowing method, a T-die method, a biaxially stretched film forming body, and a typical molding method. A molding method such as an expansion molding method or a molding method which can be found in an extrusion net of a draining net will be described below based on a general film forming method. In the present invention, a mixing method or a mixing device of a polylactic acid resin, a polyalkenyl resin, a modified polyalkenyl compound, or the like is not particularly limited, and may be continuously 10,103, 614, 00, 0, 12, 23, and 21, 21,921, processors in the industry. It is advantageous and suitable. For example, the following methods (i) and (2) 〇(1) are used to mix two or more kinds of granules at a specific ratio, and are directly used in an extrusion molding machine such as a blowing method, a T-die method, or a biaxially stretched film. A method in which a resin is placed in a funnel to melt it and form it immediately. (2) After the respective resins are melt-mixed in a molding machine of a twin-screw extruder, they are temporarily granulated, and the granules are placed in an extrusion method such as a blowing method, a T-die method, or a biaxially stretched film. The method of melting and forming the inside of the funnel of the machine. The mixing method of the above (1) can reduce the thermal deterioration of the resin, and can also be f-concentrated once in the process, so that the cost of forming is hardly increased. The mixing method of the above (2) is to granulate by melt extrusion before the molding of the film or the like is performed. Therefore, it is necessary to substantially prevent deterioration and deterioration of the polymer, and further, when the molded article is obtained, the molded article is formed. There must be two processes in the process. Therefore, the cost of forming is increased. The invention is further illustrated by the following examples, which are not intended to be limited to the examples. (Comparative Example 1) 10% by mass of a polylactic acid PLA (trade name: LACEA-4 00, manufactured by Mitsui Chemicals, Inc.) and a high-density polyethylene HDPE as a polyalkenyl resin (product name: 90% by mass of NOVATEC HF-730, manufactured by Sakamoto Polyethylene Co., Ltd., and a film having a blow ratio of 2.5 times and a thickness of 25//Π1 was formed by a blow molding machine. The molding temperature at this time was 150 to 200 ° C, and the indoor temperature was 25 ° C, which was kept constant (Comparative Example 2). The polylactic acid PLA was melt-mixed by dry mixing method (trade name: LACEA-400 1013006142-0 10014014^ single number A〇101 Page 13 of 23201221579, manufactured by Mitsui Chemicals Co., Ltd.) 2.5% by mass of HDPE as a polyalkenyl resin (trade name: NOVATEC HF-730, manufactured by Nippon Polyethylene Co., Ltd.) 5倍的厚度25 The thickness of the blower is 2. 5 times, the thickness is 25 by the blow molding machine. /zm film is used to form a film. At this time, the forming temperature was 150 to 200 ° C, and the room temperature was 25 ° C, which was kept constant. (Example 1) In a dry mixing method, a polylactic acid PLA (trade name: LACEA-400, manufactured by Mitsui Chemicals, Inc.) was added in an amount of 4.5% by mass, and HDPE was used as a polyalkenyl resin (trade name: NOVATEC HF- 730, 5% by mass, E-GMA (trade name: B0NDFAST, manufactured by Sumitomo Chemical Co., Ltd.) of modified polyalkenyl group, 2.5% by mass, using a blow molding machine The film was blown to a film having a ratio of 2.5 times and a thickness of 25/m. The forming temperature at this time is 150 to 200 ° C, and the indoor temperature is 2 5 ° C, which is kept constant. (Comparative Example 3), except that the polylactic acid (PLA) was used in an amount of 2.5% by mass, the polyalkenyl resin (HDPE) was 97.0% by mass, and the modified polyalkenyl group (E-GMA) was 0.5% by mass. The film was formed into a film in the same manner as in Example 1. (Example 2) The same as Example 1 except that 10% by mass of polylactic acid (PLA), 85% by mass of polyalkenyl resin (HDPE), and 5% by mass of modified polyalkenyl group (E-GMA) were used. The film is formed into a film. 5质量%, In addition to the use of polylactic acid (PLA) 30.0% by mass, polyalkenyl resin Li Gang #科号舰 01 1013006142-0 page 14 / 23 pages 201221579 (HDPE) 27. 5 mass%, The film was formed into a film in the same manner as in Example 1 except that the modified polyalkenyl group (E-GMA) was 42.5% by mass. (Example 4) In a dry mixing method, polylactic acid PLA (trade name: LACEA-400 'Mitsui Chemical Co., Ltd.), 1% by mass, and HDPE as a polyalkenyl resin (product name: NOVATEC HF-730) were melt-mixed. 80% by mass of a metallocene medium density polyethylene (metallocene LLDPE) (product name: EVOLUE SP2520, manufactured by Sakamoto Ethylene Co., Ltd.) as an alkenyl resin, and 5% by mass, and 5倍的厚度, 25//米的胶胶, using a blow molding machine, a blower ratio of 2. 5 times, a thickness of 25 / / m, as a modified polyalkenyl group, E-GMA (trade name: B0NDFAST, manufactured by Sumitomo Chemical Co., Ltd.) The film is formed into a film. 5质量%的聚烯基树脂树脂 (HDPE) 97 In addition to the use of polylactic acid (PLA) 2. 5 mass%, polyalkenyl resin (HDPE) 97, the molding temperature is 150 to 20 (TC, the room temperature is 25 ° C, and is kept constant. The film was formed into a film in the same manner as in Comparative Example 2 except that the modified polyalkenyl group (e-GMA) was 52.5% by mass. (Comparative Example 5) The polyalkenyl resin was HDPE ( Product name: NOVATEC UF421, manufactured by Sakamoto Polyethylene Co., Ltd.) 1 〇〇 mass %%, using a blow molding machine, a film having a blow ratio of 2.5 times and a thickness of 25 is formed. The items and the evaluation methods were compared and evaluated for the materials of the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 5. The following Tables 1 and 2 show the knots 1010016142-0OOOOHH#Single number A〇m Page I5/Total 23 Page 201221579 (Table 1) imm tt««2 实豪 W window 霄 霄 3 3 3 3 3 m/mE njmmm mmmmi vm i辄_ imm.5 stuffed flat m / m change window shoes _ rnmmmi 1. 0 0* 5 6 0. 2 0. S Poly tank concentrating 9 38 20. 7 38. 8 8· S Blowing dirty _ 2, 5 2, 5 2. 5 2. 5 2-5 雠mmmm mmmm mm 1 1*1 mmm m晡出安纤t«ll good new a good m & good mmmm Frozen surface mmm mmm mmmn thief new mmma good mu^rn *2 mm fortunately 3 瞎0, &6 0. 98 〇. se 0* 93 o. sa mmt) 172 172 172 172 1?2 mmmmi MD 43 4§ 41 40 43 TD SI 32 30 30 30 mwmmm m MD 542 500 S10 §00 §35 TD 624 605 815 S95 630 mmm MD 109 105 107 1X0 IDi TD 5i 63 60 62 61 Heat 14» (WlSmssd 13. 5 14, 5 14 0 14, 0 5以下mxt «h Submarine MUt 雠德里卿 4S. 3 4S. 3 44. 8 is. 3 43. 3 €03⁄43⁄43⁄4 2. 90 2. 98 2. 96 2. 98 2. 90 002* »^*) 3. 3 0. f 1. 3 (K 7 3. 3 * 1 No resin unevenness was observed on the surface of the film, and the compatibility was good. *2 The resin unevenness on the surface of the film is severe. *3 part of the inter-layer peeling was observed, and the glossy surface of the film surface was not observed. #单编号删1 Page 16 of 23 1013006142-0 201221579 [0005] (m) Really mmm & _ 比校阕$ 観成mmpi/B- fumm/ ilt arrogant UWB/MIk mmmm 历铁成比“Quality as me®, miscellaneous s mmm 3& secret 5/&S m雠_ 1, 42 0. 5 1· 3 A 聚 职 鼢 鼢 醯 0 0 0 0, 9 2 8. 5 0. 36 一吹继娜2· S 2. 5 2. 5 2. 5瞎*4 filial piety 4 m squirting stability m enzyme i good 鹳翳 stability a good a good a good m mmwm. m- s good name is not stable mmm Yang woven a good mmm 1. 02 0. 98 1. 04 0, 03 as 172 172 172 130 wmmm (MPa) MD 43 Bd 4§ 47 TD 34 32 37 43 mwmmm m MD 370 530 340 S10 TD β?δ 600 600 S60 mmm 〇3/ααώ MD 128 110 130 110 TD 66 58 08 ΙΟδ mmt 10. 0 Ϊ4. 0 δ. ο >15, 0 immm (Kj/g) 3T. 9 43. a 30* β 4 6* 0 002 Number 1: 2. 70 2. 9 0 2. 65 a. oo rawtaw* (10) 10. 0 3, 3 11. 7 ο. b

*4 No resin unevenness on the surface of the film was observed, and the compatibility was good. (Evaluation item and evaluation method) (1) Processability Processability was formed according to the examples. The compatibility of the discharge, the stability of the discharge of the continuous molding, the film stability, the stability of the strand, the stability of the coil, and the shape of the film opening, wrinkles or transparency of the molded article were visually observed. (2) Specific gravity The specific gravity is measured by the side method of the plastic density and specific gravity described in JIS-K-7112. (3) Melting point 40^ Single number deer 01 Page 17 of 231013006142-0 201221579 The melting point is a differential thermal analysis device according to the thermal analysis method described in JIS-K-7121 (made by Shimadzu Corporation) DSC_5 type) for measurement. (4) Tensile breaking strength and tensile breaking elongation The tensile breaking strength and the tensile breaking elongation were measured in accordance with the tensile test method described in J.B. The test piece used the No. 4 test piece recorded by jis_k_7127. (5) Tear strength The tear strength was measured in accordance with the tear test method described in JIS-K-7128 (right angle tear method). (6) Heat seal strength The heat seal strength was measured in accordance with the heat seal strength measurement method described in JIS-K-1 711. Further, the test piece was subjected to measurement of a sealed portion of a bag body which was subjected to bagging processing under the condition that the number of shots was 50 pieces/rain. The heat seal strength is an index for confirming the mechanical strength together with the tensile breaking strength 'stretch breaking elongation and tear strength. (7) Impact resistance After the bag is processed into a bag of any size, water of 1/2 capacity of the full volume is placed, and the upper and lower sides vibrate vigorously, and the bottom is peeled off or the bag body is cracked. Further, the impact resistance of Example 3 was 15 or more, and it was sufficiently tolerated. (8) Burning calories The calories burned from the raw materials used for review, namely, polylactic acid 19 KJ/g, polyethylene 46 KJ/g, modified polyalkenyl 46 KJ/g, were theoretically calculated by the following formula. Burning calories (Kj/g): = 19χΧ + 46χΥ + 46χΖ/1()() 1001401#^'^ 0101 Page 18 of 23 1013006142-0 201221579 where X is the mass of polylactic acid resin, γ: The mass portion of the dilute base resin ζ: the mass portion of the modified polyalkenyl compound (9) The amount of C0 generated during combustion C* The amount of C〇2 produced during combustion is calculated for each of the films formed in the examples and comparative examples. The amount of C〇2 produced by lkg. The calculation method is based on rHealth Digest. 14( 1 ). 1 (1 999, Ohara Haruko), according to the "(2) (from the chemical structure). Calculated by the 〇2 production amount calculation method. The calculation method is as follows. C〇2 production amount (kg-C〇2/kg-Resin) = (component quantity from petrochemical resources) x3kg/c〇+ (from biomass energy

L

The amount of the component) x2kg/CO L» In other words, according to "Health Digest. 14(1). 1 (1999, Ohara Hara)" "The amount of c〇 produced by plastic oxidative decomposition (from chemical structure) In the case of the LLDPE, the LDPE, the HDPE, and the like, the amount of the generated amount of the polyethylene is 3. Okg per ikg. Therefore, the examples 1 to 4 and the comparative examples 1 to 5 are obtained from the following calculation formula. The C 〇 2 per lkg of the molded article produced a cut-off rate (%). C〇2 produces a cut-off rate (%) = 100-((Example, comparative example, c〇 generation / 3 〇kg/c〇)χ

5〜 The poly- lactic acid resin of the combination of the polylactic acid resin, the polyalkenyl resin, and the modified polyalkenyl compound is 4. 5~ The quality of the modified polyalkenyl compound is 2. 5~45 mass%, relative to the polylactic acid resin, the modified polyalkenyl compound contains 〇. 25 More than 10 times, 1013006142-0 10014014# Single number A〇1〇l Page 19 of 23201221579 Less than 1.5 times, and made according to the conditions of 100% of the total film formation. According to the results of Tables 1 and 2, the above Examples 1 to 4 are excellent in mechanical strength and impact resistance in addition to the formation stability of the biomass-type adhesive film containing the resin component derived from the plant, and can also be achieved. 2 cuts. Further, with respect to the polylactic acid resin, the modified polyalkenyl compound contains less than 0.25 times Comparative Example 1, although the discharge safety amount or film stability is relatively good, but obtained by molding. On the surface of the film, unevenness in resin was observed, and the appearance was also unsuitable, and the impact resistance was 5 or less, and breakage occurred. In the case of Comparative Example 2, the resin unevenness on the surface of the film was not observed, and the compatibility was good, but the C〇2 reduction effect was insufficient. In the case of Comparative Example 3, the interlayer peeling phenomenon was observed between the film layers, and the glossiness of the surface of the film was not observed, and the properties of the bioenergy film which is a resin component derived from plants of the present invention were not provided. Further, in Comparative Example 3, the impact resistance was broken 10 times or less, and the c〇2 reduction effect was also insufficient. In Comparative Example 4, the C〇2 reduction effect was large, but it was observed that wrinkles were partially formed during molding, and as the polylactic acid resin component increased, the ratio of the modified polyalkenyl compound component also tends to increase, so the raw material cost 5倍以上。 The price is more than 2.5 times. Further, in Comparative Example 4, the impact resistance was broken 10 times or less. In the case of Comparative Example 5, the c〇2 deletion effect was not obtained at all. Further, the present invention is not limited to the above-described embodiments, and constituent elements may be modified and embodied in the scope of the invention without departing from the spirit and scope of the invention. Further, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the above embodiments. For example, the polylactic acid and the polyalkenyl-based composition of the embodiment are formed by a blowing method, but are not limited thereto. In other words, it is also possible to appropriately combine the components of different embodiments between 1001401#^^^ A〇101 page 20/23 pages 1013006142-0 201221579. [Simple description of the schema] [0007] None. [Main component symbol description] [0008] None.

1Q()14()14f单单A0101 Page 21 of 23 1013006142-0

Claims (1)

5〜30质量%的聚烯树脂25〜93 The polylactic acid resin is contained in an amount of 100% by mass and contains polylactic acid resin 4. 5~30% by mass, polyalkenyl resin 25~93倍倍。 The 5% or more, less than 1.5 times the amount of the polylactic acid resin. 2倍以上的20。 The poly lactic acid resin is 0. 91 times or more, 20 . 7 times or less. 3. The polylactic acid and polyalkenyl composition according to claim 1 or 2, wherein the polylactic acid resin is a resin obtained by lactating or polymerizing plant starch. 10014014^^'^^° A〇101 Page 22 of 23 1013006142-0