JP5390088B2 - Resin composition and molded article and film comprising the resin composition - Google Patents

Description

  The present invention relates to a resin composition, and a molded body and a film comprising the resin composition. In detail, moldings and films widely used in packaging materials, agricultural materials, building materials, etc. for packaging liquids, powders or solids for various foods, medicines, miscellaneous goods, etc. It relates to the resin composition for forming.

  Conventionally, paper, plastic film, aluminum foil, etc. have been used in a wide range of applications such as packaging materials, agricultural materials, and building materials for packaging liquids, powders, and solids of various foods, medicines, miscellaneous goods, etc. Has been. Among these, in particular, the plastic film is excellent in strength, water resistance, moldability, transparency, cost, and the like, and is used in many applications as a bag or a container.

  Examples of the plastic constituting the plastic film include polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. However, since these plastic films are produced from petroleum-derived raw materials, there are problems of depletion of fossil resources and problems that lead to global warming due to the generation of carbon dioxide during incineration when discarded.

  In recent years, resins produced from plants have been used for the purpose of solving the above problems. Many studies have been made on plant-derived resin raw materials, and representative examples of plant-derived resin raw materials include aliphatic polyesters such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate.

  Aliphatic polyesters having aliphatic dichanrubonic acid units and aliphatic diol units, such as polybutylene succinate and polybutylene succinate adipate, have high crystallization speed and good moldability, but the film tear strength and tensile strength are high. The elongation at break was insufficient (Patent Document 1).

As a technique for solving these problems, an attempt was made to control physical properties by mixing and using an aliphatic polyester resin and a petroleum-derived resin (Patent Document 2). However, even if these resins are simply mixed by melt blending, mechanical properties such as strength and heat resistance are hardly improved unless a majority of petroleum-derived resins are used, and conversely, there are cases where these physical properties deteriorate. Many were seen.
JP-A-8-239461 JP 2007-63297 A

  The present invention has been made in view of the above problems, a resin composition excellent in moldability, and a molded article excellent in tear strength, shrinkage, and transparency obtained by molding the resin composition. And obtaining a film.

  As a result of intensive studies to solve the above-mentioned problems, the inventor has mixed a specific proportion of a polyethylene resin having specific physical properties with an aliphatic polyester resin, and further has a specific compatibility. It was found that the above-mentioned problems can be solved by mixing an agent and an aromatic aliphatic polyester-based resin, and the following invention has been completed.

The first aspect of the present invention is an aliphatic polyester resin (A) having an elongation at break in the direction perpendicular to the resin flow (TD) of 400% or more measured by a tensile test according to JIS K6781, and a density of 0.860 g. / cm ³ or more 0.921 g / cm ³ or less, and containing MFR (190 ° C., 2.16 kg load) 0.1 g / 10 min or more 50 g / 10 min or less is polyethylene resin (B) as the main component And (A) / [(A) + (B)] as a mass ratio is 0.50 or more and 0.99 or less. Here, the “main component” refers to 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass of the component (A) and the component (B) based on the whole resin composition (100% by mass). It means containing at least 80% by mass, more preferably 80% by mass.

  The resin composition of the first aspect of the present invention is excellent in moldability, and a molded body, particularly a film, formed from the resin composition can be excellent in tear strength, heat shrinkability, and transparency. For this reason, the molded body, especially the film, should be widely used for packaging materials, agricultural materials, building materials, etc. for packaging various foods, medicines, miscellaneous liquids, powders, and solids. Can do. Hereinafter, the aliphatic polyester resin (A) may be referred to as “component (A)” and the polyethylene resin (B) may be referred to as “component (B)”.

  The resin composition of the first aspect of the present invention further includes an aliphatic polyester resin (A ′) having an elongation at break in the direction perpendicular to the resin flow (TD) of less than 400% as measured by a tensile test in accordance with JIS K6781. It is preferable that it contains. When the aliphatic polyester resin (A ′) is contained, the moldability is often improved. Hereinafter, the aliphatic polyester resin (A ′) may be referred to as “component (A ′)”. The aliphatic polyester resin (A ′) is preferably an aliphatic polyester resin mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid. Here, the “main component” refers to 70 mol% or more of an aliphatic diol and an aliphatic dicarboxylic acid based on the whole monomer unit constituting the aliphatic polyester resin (A ′) (100 mol%), Preferably it is 80 mol% or more, More preferably, it means 90 mol% or more. The aliphatic polyester resin (A ′) is preferably a polybutylene succinate resin because of its high crystallization speed. The elongation at break of the aliphatic polyester resin (A) and the aliphatic polyester resin (A ′) was measured under the same conditions.

  The resin composition of the first invention preferably further contains a compatibilizer (C) in an amount of 0.01% by mass to 30% by mass based on the entire resin composition (100% by mass). . By adding the compatibilizing agent (C), the compatibility between the component (A) and the component (B), and in some cases, the compatibility with the component (A ′) can be further improved. When the compatibility is improved, the transparency of the film is improved, and in many cases, the mechanical strength is increased, which is preferable. The compatibilizing agent (C) preferably has one of an acid anhydride group, a glycidyl group, and an ether group. By using a compatibilizing agent having these structures, the effect of improving the compatibility is increased. When a compatibilizing agent having a functional group is used, a sufficient effect can be obtained with a small amount of the compatibilizing agent added, so that it may be preferable in terms of moldability and cost. Hereinafter, the compatibilizing agent (C) may be referred to as “component (C)”.

  In the resin composition of the first aspect of the present invention, the aliphatic polyester resin (A) is preferably an aliphatic polyester resin mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid. Here, the “main component” refers to 70 mol% or more of aliphatic diol and aliphatic dicarboxylic acid based on the whole monomer unit constituting the aliphatic polyester resin (A) (100 mol%), preferably Means 80 mol% or more, more preferably 90 mol% or more. The aliphatic polyester-based resin (A) is preferable because it is a polybutylene succinate adipate-based resin in terms of improving transparency and heat shrinkability of the formed film and reducing raw material costs.

  The resin composition of the first aspect of the present invention preferably further contains the aromatic aliphatic polyester-based resin (D) in an amount of 1% by mass to 40% by mass with respect to 100% by mass of the entire resin composition. Hereinafter, the aromatic aliphatic polyester resin (D) may be referred to as “component (D)”. The addition of “component (D)” is preferable because the tear strength is improved.

  The second aspect of the present invention is a molded body made of the resin composition of the first aspect of the present invention.

  3rd this invention is a film which consists of a resin composition of the said 1st this invention.

  The fourth aspect of the present invention is based on a tensile test in which the Elmendorf tear strength in the resin flow direction (MD) measured in accordance with JIS K7128 in the case of a film having a thickness of 100 μm is 20 N / mm or more and in accordance with JIS K6781. It is a polyester film whose elongation at break in the direction perpendicular to the measured resin flow (TD) is 500% or more. In addition, since the film of 4th this invention should just have the Elmendorf tear strength of said range, when a 100-micrometer-thick film is produced using the resin composition of 1st this invention. Yes, including films of other thicknesses made using the same material.

  The resin composition of 1st this invention can be made into the resin composition excellent in the moldability by containing a component (A) and a component (B) in a predetermined | prescribed ratio, and formed with this resin composition The molded body, particularly the film, can be made excellent in tear strength, heat shrinkability, and transparency. For this reason, the molded body, especially the film, should be widely used for packaging materials, agricultural materials, building materials, etc. for packaging various foods, medicines, miscellaneous liquids, powders, and solids. Can do.

Hereinafter, the present invention will be described in detail.
<Polyethylene resin (B)>
The polyethylene resin (B) contained in the resin composition of the present invention has a density of 0.860 g / cm ^{3 to} 0.921 g / cm ³ and an MFR (190 ° C., 2.16 kg load) of 0.1 g / cm ^3. It is a polyethylene resin that is 10 minutes or more and 50 g / 10 minutes or less. Examples of the polyethylene-based resin include high-density polyethylene, high-pressure method low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and very low-density polyethylene (VLDPE). Among these, low density polyethylene is preferably used, and LLDPE and / or VLDPE is more preferably used.

  The polyethylene resin (B) of the present invention contains ethylene as a main component and may copolymerize other types of olefin components. The olefin component is preferably an α-olefin, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. Among these, 1-butene, 1-hexene and 1-octene are preferable from the viewpoint of physical properties of the resin, and 1-butene and 1-hexene are more preferable from the viewpoint of availability of raw materials and production efficiency. -Hexene is most preferred in terms of mechanical properties, thermal properties and production.

  The MFR (190 ° C., 2.16 kg load) of the polyethylene resin (B) is usually 0.1 g / 10 min or more and 50 g / 10 min or less. Further, the lower limit of MFR is preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, and most preferably 2.0 g / 10 min or more.

The lower limit of the density of the polyethylene resin (B) of the present invention is usually 0.860 g / cm ³ or more, preferably 0.870 g / cm ³ or more, more preferably 0.875 g / cm ³ or more, and most preferably 0. It is 880 g / cm ³ or more. The upper limit of the density is usually 0.921 g / cm ³ or less, preferably 0.920 g / cm ³ or less, more preferably 0.910 g / cm ³ or less, and most preferably 0.905 g / cm ³ or less. If the density is too small, it is not preferable because molding is difficult, and if the density is too large, mechanical properties such as tear strength are impaired.

  The polyethylene resin (B) of the present invention can be obtained by polymerizing ethylene (or an olefin component in some cases) using a catalyst such as a Ziegler-Natta catalyst, a chromium catalyst, or a metallocene catalyst. Among these, the polyethylene resin (B) of the present invention is preferably a polyethylene produced with a metallocene catalyst from the viewpoint of physical properties. Examples of the polymerization method include high pressure method radical polymerization, high pressure ion polymerization method, medium pressure method, low pressure method, gas phase polymerization, slurry polymerization, bulk polymerization and the like. Among them, the high pressure ionic polymerization method is preferable.

<Aliphatic polyester resin (A) or (A ')>
In the present invention, the aliphatic polyester-based resin (A) or (A ′) refers to a polyester-based resin having substantially no aromatic ring in the molecule. The aliphatic polyester resin (A) or (A ′) is preferably an aliphatic polyester resin mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid. Here, the “main component” refers to 70% aliphatic diol and aliphatic dicarboxylic acid based on the whole monomer unit constituting the aliphatic polyester resin (A) or (A ′) (100 mol%). More than mol%, preferably more than 80 mol%, more preferably more than 90 mol%.

  Specific examples of the aliphatic polyester resin (A) or (A ′) include, for example, a chain aliphatic and / or alicyclic diol unit represented by the following formula (1), and the following formula: It consists of a chain aliphatic and / or alicyclic dicarboxylic acid unit represented by (2).

—O—R ¹ —O— (1)
[In the formula (1), R ¹ represents a divalent chain aliphatic hydrocarbon group and / or a divalent alicyclic hydrocarbon group. When copolymerized, two or more types of R ¹ may be contained in the resin. ]
^-OC-R 2 -CO- (2)
[In the formula (2), R ² represents a divalent chain aliphatic hydrocarbon group and / or a divalent alicyclic hydrocarbon group. When copolymerized, two or more types of R ² may be contained in the resin. ]

  In the above formulas (1) and (2), “and” in the “divalent chain aliphatic hydrocarbon group and / or divalent alicyclic hydrocarbon group” means an aliphatic polyester resin. It means that both a divalent chain aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group may be contained in one molecule of (A) or (A ′). Hereinafter, “chain aliphatic and / or alicyclic” may be simply abbreviated as “aliphatic”.

  Although the aliphatic diol component which gives the diol unit of Formula (1) is not specifically limited, A C3-C10 aliphatic diol component is preferable and a C4-C6 aliphatic diol component is especially preferable. Specific examples include 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,4-butanediol is particularly preferable. Two or more types of aliphatic diol components can be used.

  The aliphatic dicarboxylic acid component giving the dicarboxylic acid unit of the formula (2) is not particularly limited, but an aliphatic dicarboxylic acid component having 2 to 10 carbon atoms is preferable, and an aliphatic dicarboxylic acid component having 4 to 8 carbon atoms is particularly preferable. preferable. Specific examples include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, etc. Among them, succinic acid or adipic acid is particularly preferable. Two or more types of aliphatic dicarboxylic acid components can be used.

  Furthermore, the aliphatic polyester resin (A) or (A ′) may contain an aliphatic oxycarboxylic acid unit. Specific examples of the aliphatic oxycarboxylic acid that gives an aliphatic oxycarboxylic acid unit include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3, Examples thereof include 3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, and the like, or lower alkyl esters or intramolecular esters thereof. When optical isomers are present in these, any of D-form, L-form and racemic form may be used, and the form may be any of solid, liquid or aqueous solution. Of these, lactic acid or glycolic acid is particularly preferred. These aliphatic oxycarboxylic acids can be used alone or as a mixture of two or more.

  The amount of the aliphatic oxycarboxylic acid is usually at least 0 mol%, preferably at least 0 mol%, preferably based on the whole monomer component constituting the aliphatic polyester resin (A) or (A ′) (100 mol%). It is 0.01 mol% or more, and an upper limit is 30 mol% or less normally, Preferably it is 20 mol% or less.

  In addition, the aliphatic polyester-based resin (A) or (A ′) is “trifunctional or higher aliphatic polyhydric alcohol”, “trifunctional or higher aliphatic polyvalent carboxylic acid or acid anhydride thereof” or “trifunctional”. It is preferable to copolymerize the above “aliphatic polyvalent oxycarboxylic acid” since the melt viscosity of the resulting aliphatic polyester resin (A) or (A ′) can be increased.

  Specific examples of the trifunctional aliphatic polyhydric alcohol include trimethylolpropane and glycerin. Specific examples of the tetrafunctional aliphatic polyhydric alcohol include pentaerythritol. These may be used alone or in combination of two or more.

  Specific examples of the trifunctional aliphatic polyvalent carboxylic acid or its acid anhydride include propanetricarboxylic acid or its acid anhydride. Specific examples of the tetrafunctional polycarboxylic acid or its acid anhydride include cyclopentanetetracarboxylic acid or its acid anhydride. These may be used alone or in combination of two or more.

  In addition, the trifunctional aliphatic oxycarboxylic acid includes (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, and (ii) one carboxyl group and two hydroxyl groups. Any type can be used. Specifically, malic acid or the like is preferably used. In addition, the tetrafunctional aliphatic oxycarboxylic acid includes (i) a type in which three carboxyl groups and one hydroxyl group are shared in the same molecule, and (ii) two carboxyl groups and two hydroxyl groups. And (iii) a type in which three hydroxyl groups and one carboxyl group are shared in the same molecule, and any type can be used. Specific examples include citric acid and tartaric acid. These may be used alone or in combination of two or more.

  The amount of such a tri- or higher functional compound is usually 0 mol% or more, and the lower limit is preferably 0 mol% or more, based on the whole monomer constituting the aliphatic polyester resin (A) or (A ′) (100 mol%). Is 0.01 mol% or more, and the upper limit is usually 5 mol% or less, preferably 2.5 mol% or less.

  As the aliphatic polyester resin (A), it is particularly preferable to use a polybutylene succinate adipate resin. As the aliphatic polyester resin (A ′), it is particularly preferable to use a polybutylene succinate resin.

  The aliphatic polyester resin (A) or (A ′) used in the present invention can be produced by a known method. For example, a general method of melt polymerization such as an esterification reaction and / or a transesterification reaction between the aliphatic dicarboxylic acid component and the aliphatic diol component, and a polycondensation reaction under reduced pressure, It can also be produced by a known solution heating dehydration condensation method using a solvent. Among these, from the viewpoint of economy and simplicity of the production process, a method of production by melt polymerization performed in the absence of a solvent is preferable.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction. The polymerization catalyst is generally a compound containing a group 1 to group 15 metal element excluding hydrogen and carbon in the periodic table. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. And compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates and β-diketonate complexes, and inorganic compounds such as metal oxides and halides described above, or mixtures thereof.

  In these, the metal compound containing titanium, a zirconium, germanium, zinc, aluminum, magnesium, or calcium, and those mixtures are preferable, and especially a titanium compound or a germanium compound is preferable. In addition, when the catalyst is in a melted or dissolved state at the time of polymerization, the polymerization rate is increased. Therefore, the catalyst is preferably a liquid at the time of polymerization or a compound that is soluble in an ester low polymer or polyester.

  The amount of catalyst added in the case of using a metal compound as the polymerization catalyst, the lower limit is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30000 ppm or less, preferably 1000 ppm or less, as the amount of metal relative to the produced polyester. More preferably, it is 250 ppm or less, Especially preferably, it is 130 ppm or less. If too much catalyst is used, it is not only economically disadvantageous but also lowers the thermal stability of the polymer. Conversely, if it is too little, the polymerization activity is lowered, and as a result, the polymer decomposes during polymer production. Is more likely to be triggered.

  The lower limit of the esterification reaction and / or transesterification reaction temperature between the dicarboxylic acid component and the diol component is usually 150 ° C or higher, preferably 180 ° C or higher, and the upper limit is usually 260 ° C or lower, preferably 250 ° C or lower. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon. The reaction pressure is usually normal pressure to 10 kPa, and normal pressure is preferred. The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.

In the subsequent polycondensation reaction, the lower limit of the pressure is usually 0.001 × 10 ³ Pa or more, preferably 0.01 × 10 ³ Pa or more, and the upper limit is usually 1.4 × 10 ³ Pa or less, preferably 0. The degree of vacuum is 4 × 10 ³ Pa or less. At this time, the lower limit of the reaction temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably 250 ° C. or lower. The lower limit of the reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 10 hours or less.

  As a reaction apparatus for producing the aliphatic polyester resin (A) or (A ′), a known vertical or horizontal stirred tank reactor can be used. For example, melt polymerization is carried out in two stages of esterification and / or transesterification and reduced pressure polycondensation using the same or different reactors, and a vacuum pump and a reactor are used as the reduced pressure polycondensation reactor. A method using a stirred tank reactor equipped with a evacuating pipe for decompression to be connected can be mentioned. In addition, a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and the volatile components and unreacted monomers generated during the condensation polymerization reaction are recovered by the condenser. Is preferred.

  In the present invention, the preferred range of the molar ratio of the diol component and the dicarboxylic acid component for obtaining the aliphatic polyester resin (A) or (A ′) having the desired degree of polymerization varies depending on the purpose and the type of raw material. However, the amount of the diol component relative to 1 mol of the acid component is usually at least 0.8 mol, preferably at least 0.9 mol, and the upper limit is usually at most 1.5 mol, preferably at most 1.3 mol, The amount is particularly preferably 1.2 mol or less. In addition, a urethane bond, an amide bond, a carbonate bond, an ether bond, or the like can be introduced into the aliphatic polyester resin (A) or (A ′) as long as the biodegradability is not affected.

  The aliphatic polyester resin (A ′) used in the present invention has a sufficiently high crystallization rate, and is half the exothermic peak based on crystallization when cooled at 10 ° C./min in differential scanning calorimetry. The value range is usually 15 ° C. or lower, preferably 10 ° C. or lower, particularly preferably 8 ° C. or lower. The differential scanning calorimeter is measured by using, for example, a Perkin Elmer DSC7, 10 mg of a sample is heated and melted in a nitrogen stream at a flow rate of 50 mL / min, cooled at a rate of 10 ° C./min, and accompanied with crystallization. This is done by recording the exothermic peak.

  The melt flow rate (MFR) of the aliphatic polyester-based resin (A) or (A ′) used in the present invention has a lower limit of usually 0.1 g / 10 min or more when measured at 190 ° C. and a load of 2.16 kg. The upper limit is usually 100 g / 10 min or less, preferably 50 g / 10 min or less, particularly preferably 30 g / 10 min or less.

  The elongation at break in the direction perpendicular to the resin flow (TD) of the polyester resin (A) measured by a tensile test in accordance with JIS K6781 is 400% or more, preferably 500% or more, more preferably 600% or more. More preferably, it is 700% or more. By including the aliphatic polyester resin (A) having an elongation at break of 400% or more, mechanical properties, particularly tear strength, when the resin composition is used as a film can be improved. The content of the aliphatic polyester resin (A) having an elongation at break of 400% or more in the resin composition is preferably 30% by mass or more and 90% by mass or less. The lower limit of the content is more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit of the content is more preferably 80% by mass or less, and still more preferably 70% by mass or less. If the content is 30% by mass or less, the tearing strength is unfavorable, and if it is 90% by mass or more, the moldability is unfavorable.

  The elongation at break in the direction perpendicular to the resin flow (TD) of the polyester resin (A ′) measured by a tensile test in accordance with JIS K6781 is less than 400%, preferably less than 300%, more preferably 200%. Less than, more preferably less than 100%. By including the aliphatic polyester resin (A ′) having an elongation at break of less than 400%, the rigidity of the film is improved (it is stiff). In addition, the content of the aliphatic polyester resin (A ′) having an elongation at break of less than 400% in the resin composition is preferably 0.1% by mass or more and 90% by mass or less. The lower limit of the content is more preferably 1% by mass or more, and further preferably 3% by mass or more. The upper limit of the content is more preferably 70% by mass or less, and still more preferably 50% by mass or less. If the content is too small, the moldability may be deteriorated, and if the content is too large, the mechanical properties are undesirably lowered.

  The ratio (mass ratio) of the aliphatic polyester resin (A) to the total amount of the aliphatic polyester resin (A) and the polyethylene resin (B) "(A) / [(A) + (B)]" 0.50 or more and 0.99 or less. The upper limit of (A) / [(A) + (B)] is preferably 0.95 or less, more preferably 0.90 or less, and even more preferably 0.85 or less. The lower limit is preferably 0.60 or more, more preferably 0.70 or more. If (A) / [(A) + (B)] is too low, a sufficient elongation at break cannot be obtained, and it is not preferable, and if it is too high, the tear strength is lowered, which is not preferable.

<Compatibilizer (C)>
The resin composition of the present invention may contain a compatibilizer (C). A compatibilizing agent is an additive that improves compatibility when mixing incompatible dissimilar resins. By adding the compatibilizing agent (C), the compatibility between the component (A) and the component (B), and in some cases, the compatibility with the component (A ′) can be further improved. When the compatibility is improved, the transparency of the film is improved, and in many cases, the mechanical strength is increased, which is preferable.

  It is preferable to add the compatibilizer (C) in an amount of 0.01% by mass or more and 30% by mass or less based on the total resin composition (100% by mass). The lower limit of the addition amount is more preferably 0.1% by mass or more, and further preferably 1% by mass or more. The upper limit of the addition amount is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

  Examples of the compatibilizer (C) include a polymer compatibilizer, a low molecular organic compound, an inorganic compound, an organic-inorganic composite, and the like. In view of the physical properties of the molded product, a polymer type compatibilizer is more preferable from the viewpoint of the molding process. Further, the compatibilizer (C) preferably has one of an acid anhydride group, glycidyl group, and ether group, and a polymer type compatibilizer having any of these structures is more preferable. preferable. By using a compatibilizing agent having these structures, the effect of improving the compatibility is increased. When a compatibilizing agent having a functional group is used, a sufficient effect can be obtained with a small amount of the compatibilizing agent added, so that it may be preferable in terms of moldability and cost.

  Polymeric compatibilizers include polyester, polyolefin, polyamide, polyether, polycarbonate, acrylic, styrene, urethane, polyacetal, olefin elastomer, unsaturated aliphatic elastomer, hydrogenated Examples thereof include resins such as unsaturated aliphatic elastomers, and two or more kinds of these blocks, grafts, or random copolymers. A polar group may be introduced into the molecule by further adding an unsaturated fatty acid anhydride to these copolymers. Maleic anhydride is preferably used as the unsaturated fatty acid anhydride to be added.

  Among these, polyester-based, polyolefin-based, polyamide-based, polyether-based, acrylic-based, styrene-based, olefin-based elastomers, unsaturated aliphatic elastomers, hydrogenated unsaturated aliphatic elastomers, and the co-polymerization of two or more of these More preferred are coalesced or the like, and more preferred are polyolefin-based, polyamide-based, polyether-based, acrylic-based, styrene-based, hydrogenated unsaturated aliphatic elastomers, and copolymers of two or more thereof.

  Examples of the polyester-based compatibilizer (C) include aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, or polybutylene succinate, polybutylene succinate adipate, polylactic acid, polycaprolactone, and poly-3-hydroxybutyrate. Other than component (A) and component (A ′), such as a polyester block or random or graft copolymer (for example, a block copolymer of polybutylene succinate and polyethylene) containing a structure such as Aliphatic polyesters may be mentioned.

  Examples of the polyolefin-based compatibilizer (C) include components such as high-density polyethylene, high-pressure method low-density polyethylene, linear low-density polyethylene (LLDPE), block containing a structure such as polypropylene, or random or graft copolymer. Examples include polyolefin resins other than (B). Examples of the polyamide-based compatibilizer (C) include 6 nylon, 6, 6 nylon, and 12 nylon. Examples of the polyether-based compatibilizer (C) include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of the styrene type include polystyrene, poly p-methyl styrene, poly α-methyl styrene and the like. Examples of the olefin elastomer include ethylene propylene random copolymer and poly 1-butene. Examples of the unsaturated aliphatic elastomer include polybutadiene, polyisoprene, SBS, and SIS. Examples of the hydrogenated unsaturated aliphatic elastomer include SEBS and SEPS. Among polyolefin-based, polyamide-based, polyether-based, acrylic-based, styrene-based, hydrogenated unsaturated aliphatic elastomers and two or more types of these copolymers, polyolefin / glycidyl acrylate copolymers, Examples include polyolefin / glycidyl methacrylate copolymer, polyolefin / polyether copolymer, polyether ester amide, SEBS, maleic anhydride-modified SEBS, and the like.

<Aromatic aliphatic polyester resin (D)>
The resin composition of the present invention may contain an aromatic aliphatic polyester resin (D). The aromatic aliphatic polyester resin (D) includes an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, a chain aliphatic and / or alicyclic diol unit, and an aromatic dicarboxylic acid. The unit content is from 5 mol% to 60 mol% based on the total amount of aliphatic dicarboxylic acid units and aromatic dicarboxylic acid units (100 mol%). Specifically, for example, an aliphatic diol unit represented by the following formula (3), an aliphatic dicarboxylic acid unit represented by the following formula (4), and an aroma represented by the following formula (5) Group dicarboxylic acid unit as an essential component.

—O—R ³ —O— (3)
[In the formula (3), R ³ represents a divalent chain aliphatic hydrocarbon group and / or a divalent alicyclic hydrocarbon group, and is not limited to one type when copolymerized. ]
—OC—R ⁴ —CO— (4)
[In the formula (4), R ⁴ represents a direct bond or a divalent chain aliphatic hydrocarbon group and / or a divalent alicyclic hydrocarbon group, and is 1 when copolymerized. It is not limited to species. ]
—OC—R ⁵ —CO— (5)
[In Formula (5), R ⁵ represents a divalent aromatic hydrocarbon group, and is not limited to one type when copolymerized. ]

  The diol component giving the diol unit of the formula (3) is usually one having 2 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexane. Examples include dimethanol. Among these, diols having 2 to 4 carbon atoms are preferable, ethylene glycol and 1,4-butanediol are more preferable, and 1,4-butanediol is particularly preferable.

  The dicarboxylic acid component that gives the dicarboxylic acid unit of the formula (4) usually has 2 to 10 carbon atoms, and examples thereof include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Among these, succinic acid or adipic acid is preferable.

  Examples of the aromatic dicarboxylic acid component that gives the aromatic dicarboxylic acid unit of the formula (5) include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like, among which terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable. preferable. Moreover, aromatic dicarboxylic acid in which a part of the aromatic ring is substituted with a sulfonate is exemplified. Two or more types of aliphatic dicarboxylic acid components, aliphatic diol components, and aromatic dicarboxylic acid components can be used.

  The aromatic aliphatic polyester resin (D) in the present invention may contain an aliphatic oxycarboxylic acid unit. Specific examples of the aliphatic oxycarboxylic acid that gives an aliphatic oxycarboxylic acid unit include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3, Examples include 3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, or a mixture thereof. Furthermore, these lower alkyl esters or intramolecular esters may be used. When optical isomers are present in these, any of D-form, L-form and racemic form may be used, and the form may be any of solid, liquid or aqueous solution. Among these, lactic acid or glycolic acid is preferable. These aliphatic oxycarboxylic acids can be used alone or as a mixture of two or more.

  The amount of the aliphatic oxycarboxylic acid has a lower limit of usually 0 mol% or more, preferably 0.01 mol% or more, and an upper limit of usually all components constituting the aromatic aliphatic polyester resin (D). 30 mol% or less, preferably 20 mol% or less. The aromatic aliphatic polyester resin (D) can be produced by the same production method as the aliphatic polyester resin (A) or (A ′).

  The melt flow rate (MFR) of the aromatic aliphatic polyester resin (D) used in the present invention has a lower limit of usually 0.1 g / 10 min or more when measured at 190 ° C. and a load of 2.16 kg. Is usually 100 g / 10 min or less, preferably 50 g / 10 min or less, particularly preferably 30 g / 10 min or less.

  The content of the aromatic aliphatic polyester resin (D) described above is preferably 1% by mass or more and 40% by mass or less based on the entire resin composition (100% by mass). The lower limit of the content is more preferably 5% by mass or more, and still more preferably 10% by mass or more. The upper limit of the content is more preferably 30% by mass or less, and still more preferably 20% by mass or less. When there is too much content of aromatic aliphatic polyester-type resin (D), the transparency at the time of setting it as heat shrinkability and a film will fall, and it is unpreferable. Moreover, when there are too few, sufficient addition effect cannot be expressed.

<Inorganic filler>
You may mix | blend an inorganic filler with the resin composition of this invention. Examples of such inorganic fillers include silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, wollastonite. , Calcined perlite, "silicates such as calcium silicate and sodium silicate", hydroxides such as aluminum oxide, magnesium carbonate, calcium hydroxide, ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, etc. Can be mentioned. These may be used individually by 1 type, and may mix and use 2 or more types.

  The amount of the inorganic filler contained in the resin composition of the present invention is not particularly limited, but the inorganic filler is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition, and 3 parts by mass. The content is more preferably 20 parts by mass or less and particularly preferably 5 parts by mass or more and 15 parts by mass or less. If the amount of the inorganic filler is too small, the effect of improving the mechanical properties may be reduced. On the other hand, if the amount is too large, the moldability and impact resistance may be deteriorated.

<Organic filler>
Examples of the organic filler include raw starch, processed starch, pulp, chitin / chitosan, coconut powder, bamboo powder, bark powder, and powders such as kenaf and straw. These may be used individually by 1 type, and may mix and use 2 or more types. The content of the organic filler in the resin composition is preferably 60 parts by mass or less with respect to 100 parts by mass of the resin composition.

  Among them, as the organic filler, starch such as raw starch and processed starch is preferable in that the effect of improving the tear strength is high. The starch is preferably contained in an amount of 5 parts by weight or more and 60 parts by weight or less, more preferably 10 parts by weight or more and 40 parts by weight or less, and more preferably 15 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the resin composition. It is particularly preferable that the content is not more than part by mass. If the amount of starch is too small, the effect of improving the tear strength may be low. On the other hand, if the amount is too large, the hygroscopicity may be high and the product life may be shortened.

<Various additives>
The resin composition in the present invention can further contain various conventionally known additives. Examples of additives include crystal nucleating agents, antioxidants, anti-blocking agents, ultraviolet absorbers, light-resistant agents, plasticizers, heat stabilizers, colorants, flame retardants, mold release agents, antistatic agents, and antifogging agents. , Surface wettability improvers, incineration aids, pigments, lubricants, dispersion aids, various surfactants, slip agents, hydrolysis inhibitors and the like. These may be used individually by 1 type, and may mix and use 2 or more types. Among these, it is particularly preferable to add a slip agent and an antiblocking agent.

  The antifogging agent may be previously kneaded into the resin, or may be applied to the surface of the molded article after molding. Specifically, the antifogging agent used is preferably an ester surfactant of a saturated or unsaturated aliphatic carboxylic acid having 4 to 20 carbon atoms and a polyhydric alcohol. Examples of the slip agent include unsaturated fatty acid amides and unsaturated fatty acid bisamides composed of unsaturated fatty acids having 6 to 30 carbon atoms, most preferably erucic acid amide.

  Examples of the anti-blocking agent include saturated fatty acid amides having 6 to 30 carbon atoms, saturated fatty acid bisamides, methylol amides, ethanol amides, natural silicas, synthetic silicas, synthetic celite, talc and the like.

  Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxyphenyl) -2-n-butyl-bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, 2- (3,5-di-tert-butyl-4-hydroxyphenyl) -2-n-butyl-bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) malonate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl-bis (2,2,6,6-tetramethyl) -4-piperidyl) malonate, 2- 3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, mixed (2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed (1,2,2,6, 6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β '− Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro [5.5] undecane] diethyl} -1,2,3,4-butanetetracarboxylate, mixed {1,2,2 , 6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro [5.5] undecane] diethyl}- 1,2,3,4-butanetetracarboxylate, 1,2-bis (3-oxo-2,2,6,6-tetramethyl-4-piperidyl) ethane, 1- (3,5-di-t -Butyl-4-hydroxyphenyl) -1,1-bis (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) pentane, poly [1-oxyethylene (2,2,6,6-tetra Methyl-1,4-piperidyl) oxys Sinyl], poly [2- (1,1,4-trimethylbutylimino) -4,6-triazinediyl- (2,2,6,6-tetramethyl-4-piperidyl) iminohexamethylene- (2,2 , 6,6-tetramethyl-4-piperidyl) imino], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (2,2,6,6- Tetramethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and its N-methyl compound, succinic acid and 1- (2-hydroxyethyl) -4-hydroxy-2,2, Examples include polycondensates with 6,6-tetramethylpiperidine.

  Among these, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl- Bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate is particularly preferred.

  As the UV absorber that may be added to the resin composition of the present invention, among the UV absorbers such as benzophenone-based, benzotriazole-based, salicylic acid-based, and cyanoacrylate-based, a benzotriazole-based UV absorber is preferable. Specifically, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-hexyloxy-phenol.

  Antioxidants that may be added to the resin composition of the present invention include BHT, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-α, α ′, α ″-(mesitylene-2,4,6 -Triyl) tri-p-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [(4-tert-butyl-3-hydroxy- 2,6-Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di-tert-butyl- 4 -Hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, calcium diethylbis [{3,5-bis (1,1-dimethylethyl) -4-hydroxy Phenyl} methyl] phosphonate, bis (2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethylphenyl) ethane, N, N′-hexane-1,6-diylbis [3 Hindered phenolic antioxidants such as-(3,5-di-tert-butyl) -4-hydroxyphenyl] propionamide, tridecyl phosphite, diphenyldecyl phosphite, tetrakis (2,4-di-tert- Butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl)- -Methylphenyl] ethyl ester phosphorous acid, phosphorus antioxidants such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3-hydroxy-5,7-di-tert-butyl- Examples include lactone-based antioxidants such as reactive products of furan-2-one and xylene, sulfur-based antioxidants such as dilauryl thiodipropionate, distearyl thiodipropionate, and mixtures of two or more thereof. Of these, hindered phenolic antioxidants are preferably used.

  Preferred hindered phenolic antioxidants include Irganox 3790, Irganox 1330, Irganox 1010, Irganox 1076, Irganox 3114, Irganox 1425WL, Irganox 1098, Irganox HP2225FL, Irganox HP2341, Irgaphos XP-30. (Above, manufactured by Ciba Specialty Chemicals Co., Ltd.) and Sumilyzer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.) are used. The most preferred antioxidant is Irganox 3790 (1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4, 6 (1H, 3H, 5H) -trione), Irganox 1330 (3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-α, α ′, α ″-(mesitylene-2) , 4,6-triyl) tri-p-cresol).

  The addition amount of these additives is usually 0.001% by mass or more and 10% by mass or less based on the whole resin composition (100% by mass). The lower limit of the addition amount is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. The upper limit of the addition amount is preferably 5% by mass or less, more preferably 3% by mass or less. Moreover, the resin composition of this invention can also mix | blend a freshness keeping agent, an antibacterial agent, etc. as a functional additive.

  Examples of the terminal blocking agent include carbodiimide compounds, epoxy compounds, oxazoline compounds, etc. Among them, carbodiimide compounds are preferably used.

<Carbodiimide compound>
In the present invention, a carbodiimide compound can be suitably used mainly for the purpose of suppressing hydrolysis due to moisture in the atmosphere. The carbodiimide compound used is a compound (including a polycarbodiimide compound) having one or more carbodiimide groups in the molecule, and such a carbodiimide compound uses, for example, an organophosphorus compound or an organometallic compound as a catalyst, It can be synthesized by subjecting an isocyanate compound to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of 70 ° C. or higher.

Among the above carbodiimide compounds, the monocarbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, and di-β-naphthylcarbodiimide. Etc. can be illustrated. Of these, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferred because they are easily available industrially.
Examples of the polycarbodiimide compound include U.S. Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, J. Pat. Org. Chem. 28, p2069-2075 (1963), and Chemical Review 1981, 81, No. 4, p. 619-p. What was manufactured by the method described in 621 grade | etc., Can be used.

  In the present invention, a polycarbodiimide compound may be used. The lower limit of the degree of polymerization is 2 or more, preferably 4 or more, and the upper limit is usually 40 or less, preferably 20 or less. When the degree of polymerization is too large, dispersibility in the composition becomes insufficient, and for example, it may cause poor appearance in an inflation film.

  The carbodiimide compound may be added during the preparation of the resin composition to be described later, the aliphatic polyester resin (A) or (A ′), the aromatic aliphatic polyester resin (D), or the compatibilizer (C). One or two of these polyesters may be kneaded and mixed with all the components of the resin composition by dry blending with other components at the time of molding. Alternatively, a master batch of a high concentration carbodiimide compound is prepared with the aliphatic polyester resin (A) or (A ′) and / or the aromatic aliphatic polyester resin (D), and the carbodiimide compound has a predetermined concentration during molding. As described above, the aliphatic polyester resin (A) or (A ′) and / or the aromatic aliphatic polyester resin (D) may be dry blended and diluted.

<Other ingredients>
The resin composition of the present invention includes biodegradable resins and natural products such as polylactic acid, polycaprolactone, polyamide, polyvinyl alcohol, cellulose ester and the like, starch, cellulose, paper, wood, and the like as long as the effects of the present invention are not impaired. Fine powders of animal / plant substances such as flour, chitin / chitosan, coconut shell powder, walnut shell powder, or a mixture thereof can be blended.

<Kneading and molding method>
(Kneading method): In the present invention, all conventionally known mixing / kneading techniques can be applied. As the mixer, a horizontal cylindrical type, V-shaped, double-cone type mixer, a blender such as a ribbon blender or a super mixer, various continuous mixers, or the like can be used. Moreover, as a kneading machine, a batch type kneading machine such as a roll or an internal mixer, a one-stage type, a two-stage type continuous kneading machine, a twin screw extruder, a single screw extruder, or the like can be used.

  Although the preparation method of the resin composition of this invention is not specifically limited, The method of melt-mixing the blended raw material chip | tip with the same extruder, the method of mixing after melt | dissolving with each separate extruder, etc. are mentioned. In addition, it is possible to obtain the molded body at the same time as adjusting the resin composition by supplying each raw material chip directly to the molding machine. When the components of the present invention are mixed and melted by heating, various additives, inorganic fillers, organic fillers, the above-mentioned “other components”, a method of adding other polyesters, and the like are included. . At this time, blending oil or the like can also be used for the purpose of uniformly dispersing the various additives.

  (Molding method): The resin composition in the present invention can be subjected to molding by various molding methods applied to general-purpose plastics. Examples of the molding method include compression molding (compression molding, laminate molding, stampable molding), injection molding, extrusion molding, and coextrusion molding (film molding by inflation method and T-die method, laminate molding, pipe molding, electric wire / cable molding. , Profile molding), hollow molding (various blow molding), calendar molding, foam molding (melt foam molding, solid phase foam molding), solid molding (uniaxial stretching molding, biaxial stretching molding, roll rolling molding, stretch oriented nonwoven fabric Examples include molding, thermoforming (vacuum forming, pressure forming), plastic working, powder forming (rotary forming), various non-woven fabric forming (dry method, adhesion method, entanglement method, spunbond method, etc.), among others, extrusion forming, Injection molding, foam molding, and hollow molding are preferably applied, and specific shapes are preferably applied to films, containers, and fibers.

  Also, these molded products are provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubricating functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. For the purpose, secondary processing can be performed for various purposes. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating) and the like.

<Physical properties>
The Elmendorf tear strength in the resin flow direction (MD) of the film (thickness 100 μm) molded from the resin composition of the present invention measured in accordance with JIS K7128 is preferably 20 N / mm or more, more preferably. 30 N / mm or more, more preferably 40 N / mm or more. If the Elmendorf tear strength is too small, there are practical problems such as leakage and breakage of contents depending on the use such as packaging materials, which is not preferable. Further, the elongation percentage in the direction perpendicular to the resin flow (TD) of the film molded from the resin composition of the present invention measured by a tensile test in accordance with JIS K6781 is preferably 500% or more, more preferably 550% or more. More preferably, it is 600% or more, and particularly preferably 650% or more.

<Application>
The resin composition of the present invention is excellent in moldability, and is excellent in surface characteristics and mechanical characteristics of a molded body formed from the resin composition. For this reason, the molded body made of the resin composition of the present invention has a wide range of uses such as packaging materials, agricultural materials, and building materials for packaging various foods, medicines, miscellaneous liquids, powders, and solids. Is preferably used. Specific applications include injection molded products (eg, fresh food trays, fast food containers, outdoor leisure products, etc.), extruded products (films, eg fishing lines, fishing nets, vegetation nets, water retaining sheets, etc.), hollow Examples include molded products (bottles, etc.). In addition, other agricultural films, coating materials, fertilizer coating materials, laminated films, plates, stretched sheets, monofilaments, nonwoven fabrics, flat yarns, staples, crimped fibers, striped tape, split yarns, composite fibers, blow bottles, Foam, shopping bag, garbage bag, compost bag, cosmetic container, detergent container, bleach container, rope, binding material, hygiene cover stock material, cold box, cushion material film, multifilament, synthetic paper, surgery for medical use Examples thereof include DDS such as thread, suture, artificial bone, artificial skin, and microcapsule, and wound dressing.

  Furthermore, for information electronic materials such as toner binders and thermal transfer ink binders, automotive interior parts such as electrical product casings, instrument panels, sheets and pillars, and automotive exterior structural materials such as bumpers, front grills and wheel covers. Can be used. Among them, more preferably, packaging materials, such as packaging films, bags, trays, bottles, cushioning foams, fish boxes, and the like, and agricultural materials such as mulching films, tunnel films, house films, sun covers. , Herbicidal sheets, cocoon sheets, germination sheets, vegetation mats, nursery beds, flower pots and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.

<Measurement method of tear strength>
The Elmendorf tear strength was measured according to JIS K7128.
<Measurement method of yield strength, breaking strength, tensile breaking elongation>
It measured by the tensile test based on JISK6781.
<MFR>
Melt flow rate (g / 10 min): Measured at 190 ° C. and 2.16 kg load.
<Heat shrinkability>
A film molded in hot water at 100 ° C. was placed and left for 3 minutes. The degree of deformation at that time was confirmed visually. The results are shown in Table 1. Heat shrinkability ◎: Very large, ○: Large, △: Medium, ×: Small <Transparency>
Table 1 shows the results of visual observation of the transparency of the molded film. ◎: Very good transparency, ○: Good transparency, ×: Inferior transparency

<Examples 1 to 25>
Biaxially mixed with aliphatic polyester resin (A) and polyethylene resin (B), if necessary, compatibilizer (C), and aromatic aliphatic polyester resin (D) at the mass ratio shown in Table 1. It knead | mixed at 180-190 degreeC with the extruder. As the aliphatic polyester resin (A), PBSA resin (AD92WN manufactured by Mitsubishi Chemical Corporation) was used. As the aliphatic polyester resin (A ′), a PBS resin (AZ91TN manufactured by Mitsubishi Chemical Corporation) was used. Kernel KS240T (manufactured by Nippon Polyethylene Co., Ltd .: density 0.880, MFR = 2.2) and / or kernel KS260 (manufactured by Nippon Polyethylene Co., Ltd .: density 0.902, MFR = 2.2) are used as the polyethylene resin (B). It was.

  As compatibilizer (C), Tuftec M1911, M1913, M1943 manufactured by Asahi Kasei Co., Ltd., Bond First CG5004, CG5001 manufactured by Sumitomo Chemical Co., Ltd., Pelestat NC6321, 300, VH230, 201 manufactured by Sanyo Kasei Co., Ltd. were used. Moreover, as the aromatic aliphatic resin (D), Ecoflex manufactured by BASF was used. The resin obtained by kneading with a twin screw extruder was dried in a hot air dryer at 70 ° C. for 10 hours under a nitrogen stream. The dried resin was subjected to inflation molding at 160 ° C. to obtain a film having a tough tear strength with a thickness of 100 μm. The evaluation results are shown in Table 1.

<Comparative Examples 1-8>
A 100 μm film was obtained by kneading, drying and inflation molding with a twin screw extruder in the same manner as in Examples 1 to 25 with the mass ratio shown in Table 1 (however, only Comparative Examples 1 and 2 were films having a thickness of 20 μm. Molded.) The evaluation results are shown in Table 1.

  As shown in Comparative Examples 1 and 2 in Table 1, the elongation at break in the TD direction of the aliphatic polyester resin (A) is 820% (Comparative Example 2). The elongation at break in the TD direction of the aliphatic polyester resin (A ′) is 40% (Comparative Example 1).

  As shown in Table 1, the film made of the resin composition of the present invention has a significantly improved Elmendorf tear strength in the MD (resin flow direction) direction, and according to the present invention, a film having excellent mechanical properties can be obtained.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, it can be changed as appropriate without departing from the scope or spirit of the invention that can be read from the claims and the entire specification, and a resin composition accompanied by such a change, and a molded body and a film made of the resin composition are also included. It should be understood as being included within the scope of the present invention.

  The resin composition of the present invention is excellent in moldability, and a molded body formed from the resin composition, particularly a film, is excellent in tear strength, heat shrinkability, and transparency. It can be widely used as a packaging material, an agricultural material, a building material, etc. for wrapping products, powders and solids.

Claims (12)

Aliphatic polyester-based resin (A) having a elongation at break in the direction perpendicular to the resin flow (TD) of 400% or more measured by a tensile test in accordance with JIS K6781 and a density of 0.860 g / cm ^{3 to} 0.910 a polyethylene-based resin (B) having a g / cm ³ or less and MFR (190 ° C., 2.16 kg load) of 0.1 g / 10 min or more and 50 g / 10 min or less as a main component,
(A) / [(A) + (B)] is 0.50 or more and 0.99 or less as mass ratio, The resin composition characterized by the above-mentioned. Furthermore, the resin composition of Claim 1 containing the aliphatic polyester-type resin (A ') whose breaking elongation of a perpendicular direction (TD) is less than 400% with respect to the resin flow measured by the tensile test based on JISK6781. object. The resin composition according to claim 2, wherein the aliphatic polyester resin (A ') is an aliphatic polyester resin mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid. The resin composition according to claim 2 or 3, wherein the aliphatic polyester resin (A ') is a polybutylene succinate resin. The resin composition according to any one of claims 1 to 4, wherein the compatibilizing agent (C) is contained in an amount of 0.01% by mass to 30% by mass based on 100% by mass of the entire resin composition. The resin composition according to claim 5, wherein the compatibilizing agent (C) has a structure of any one of an acid anhydride group, a glycidyl group, and an ether group. The resin composition according to any one of claims 1 to 6, wherein the aliphatic polyester resin (A) is an aliphatic polyester resin mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid. The resin composition according to any one of claims 1 to 7, wherein the aliphatic polyester resin (A) is a polybutylene succinate adipate resin. Furthermore, the resin composition in any one of Claims 1-8 which contains an aromatic aliphatic polyester-type resin (D) 1 mass% or more and 40 mass% or less by making the whole resin composition into 100 mass%. The molded object which consists of a resin composition in any one of Claims 1-9. The film which consists of a resin composition in any one of Claims 1-9. When the film has a thickness of 100 μm, the Elmendorf tear strength in the resin flow direction (MD) measured in accordance with JIS K7128 is 20 N / mm or more, and the direction perpendicular to the resin flow measured by a tensile test in accordance with JIS K6781 The polyester film according to claim 11, wherein the elongation at break of (TD) is 500% or more.