JP5292868B2 - Resin composition and molded article and film comprising the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having a strong tearing strength, good biodegradability, good moldability and good surface characteristics, and to provide a molded article of the same. <P>SOLUTION: This resin composition is provided by containing a 20 to 94.9 mass% aliphatic polyester-based resin (A), a 5-60 mass% aromatic and aliphatic polyester-based resin (B) and a 0.1 to 40 mass% compatibilizer (C) having a polar group and/or an aromatic group. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a resin composition and a molded article and a film made of the resin composition. Specifically, the resin composition containing a specific compatibilizing agent and used for agricultural films, garbage bags, compost bags, shopping bags, shopping bags, food packaging materials, food containers, etc. comprising the resin composition. It relates to possible molded articles and films.

  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, they have the problem of depletion of fossil resources and the problem of global warming due to carbon dioxide generated during incineration. Also, most plastics are durable in the environment, so that their shape is maintained when discarded, and waste problems such as environmental pollution and lack of landfill are becoming serious.

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

  Examples of the biodegradable resin include aliphatic polyesters or aromatic aliphatic polyesters such as polylactic acid, polybutylene succinate, polybutylene succinate adipate, polycaprolactone, polybutylene terephthalate adipate, and polybutylene terephthalate succinate. However, these aliphatic polyesters and aromatic aliphatic polyesters have insufficient mechanical properties such as tear strength of the film (Patent Document 1).

As a technique for solving these problems, Patent Document 2 attempts to control physical properties by mixing an aliphatic polyester resin and an aromatic aliphatic polyester resin, but the mechanical properties have not been improved yet. It was insufficient. Therefore, a biodegradable resin having further improved mechanical properties while maintaining moldability and surface characteristics is desired.
JP-A-8-239461 JP 2005-015606 A

  The present invention has been made in view of the above problems, and it is an object of the present invention to provide a resin composition having high tear strength, good biodegradability, good moldability and surface characteristics, and a molded product thereof. To do.

  As a result of studying the above problems, the present inventors have found that a resin composition containing a specific compatibilizing agent (C) can solve the above problems, and have completed the following present invention.

That is, the first aspect of the present invention comprises an aliphatic polyester resin (A), an aromatic aliphatic polyester resin (B), and a compatibilizer (C) having an epoxy group and / or an aromatic group. It is a resin composition to be contained, and the mass ratio of each component to the entire resin composition is 20 to 94.9% aliphatic polyester resin (A), 5 to 60% aromatic aliphatic polyester resin (B). The resin composition is characterized in that it is 0.1 to 40% of a compatibilizer (C) having an epoxy group and / or an aromatic group to solve the above-mentioned problems.

In this embodiment, the compatibilizer (C) is arbitrary preferred that a block copolymer and / or graft copolymer.

  In this embodiment, the aliphatic polyester-based resin (A) is mainly composed of an aliphatic dicarboxylic acid and an aliphatic diol, and includes “trifunctional or higher aliphatic polyhydric alcohol” and “trifunctional or higher functional fat. The raw material constituting the aliphatic polyester-based resin (A) is composed of “polyhydric carboxylic acid or acid anhydride thereof” and “at least one compound selected from tri- or higher functional polyhydric oxycarboxylic acids”. On the other hand, it is also preferable that the resin be copolymerized by 0.0001 to 1 mol%.

  In this embodiment, the aromatic aliphatic polyester resin (B) is preferably polybutylene terephthalate adipate and / or polybutylene terephthalate succinate.

The second aspect of the present invention contains an aliphatic polyester resin (A), an aromatic aliphatic polyester resin (B), and a compatibilizer (C) having an epoxy group and / or an aromatic group. A method for producing a resin composition molded article, comprising: a compatibilizer (C), an aliphatic polyester resin (A) and / or an aromatic aliphatic polyester before the step of molding the resin composition molded article. The present invention provides a method for producing a resin composition molded article, comprising a step of melt-kneading a resin-based resin (B) at a temperature higher than a temperature for molding a resin composition molded article. is there.

  According to a third aspect of the present invention, there is provided a resin composition molded article comprising the resin composition of the first aspect (including the preferred aspect) as a main component to solve the above-mentioned problems. It is.

  According to a fourth aspect of the present invention, there is provided a film characterized by including the resin composition of the first aspect (including the preferred aspect) as a main component to solve the above problems.

  In the third and fourth aspects, “containing the resin composition as a main component” means that the content of the resin composition is at least 50% by mass or more of the total mass of the molded article or film. .

  According to the present invention, it is possible to obtain a resin composition excellent in tensile strength and tear strength and having good moldability. For this reason, the molded body obtained from the resin composition, particularly the film, is a packaging material, agricultural material, and building material for packaging various foods, medicines, miscellaneous liquids, powders, and solids. It can be used widely.

  The resin composition of the present invention comprises at least an aliphatic polyester resin (A), an aromatic aliphatic polyester resin (B), and a compatibilizer (C). Hereinafter, each component and a method for producing the resin composition will be described in detail.

<Aliphatic polyester resin (A)>
In the present invention, the aliphatic polyester-based resin is mainly composed of an aliphatic monomer such as an aliphatic oxycarboxylic acid or a mixture of an aliphatic diol and an aliphatic dicarboxylic acid, and has an aromatic ring in the molecule. A polyester-based resin that does not exist. Here, the “main raw material” means that the proportion of the aliphatic monomer component is 95 mol% or more, preferably 97 mol, based on the whole monomer unit constituting the aliphatic polyester resin (100 mol%). % Or more, more preferably 99 mol% or more.

  Specific examples of the aliphatic oxycarboxylic acid used as a raw material for the aliphatic polyester resin (A) include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2- Examples thereof include hydroxy-3,3-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.

  As the aliphatic polyester resin (A) used in the present invention, an aliphatic polyester resin (A ′) containing an aliphatic diol and an aliphatic dicarboxylic acid as main raw materials is particularly preferable. Specific examples of the aliphatic polyester-based resin (A ′) include a chain aliphatic and / or alicyclic diol unit represented by the following formula (1) and the following formula (2). It consists of the chain aliphatic and / or alicyclic dicarboxylic acid units represented.

—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. This means that both a divalent chain aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group may be contained in one molecule. Hereinafter, “chain aliphatic and / or alicyclic” may be simply abbreviated as “aliphatic”.

  The aliphatic diol component giving the diol unit of the formula (1) is not particularly limited, but an aliphatic diol component having 2 to 10 carbon atoms is preferable, and an aliphatic diol component having 4 to 6 carbon atoms is particularly preferable. Specific examples include ethylene glycol, 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 aliphatic dicarboxylic acid components can also be used.

  The aliphatic polyester resin (A ′) mainly composed of aliphatic diol and aliphatic dicarboxylic acid may also contain an aliphatic oxycarboxylic acid unit. Specific examples of the aliphatic oxycarboxylic acid providing the aliphatic oxycarboxylic acid unit include those described above as the raw material of the aliphatic polyester resin (A). The preferred amount of the aliphatic oxycarboxylic acid to be contained in the aliphatic polyester resin (A ′) mainly comprising an aliphatic diol and an aliphatic dicarboxylic acid is the monomer constituting the aliphatic polyester resin (A ′). The lower limit is usually 0 mol% or more, preferably 0.01 mol% or more, and the upper limit is usually 30 mol% or less, preferably 20 mol% or less, based on the whole component (100 mol%).

  The aliphatic polyester-based resin (A ′) is composed of “a trifunctional or higher aliphatic polyhydric alcohol”, “a trifunctional or higher aliphatic polyvalent carboxylic acid or acid anhydride thereof”, “a trifunctional or higher aliphatic. It is preferable that at least one of the “polyoxycarboxylic acids” is copolymerized because the melt viscosity of the resulting aliphatic polyester resin 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 polyvalent carboxylic 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. Both types 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 0.0001 mol% or more, preferably 0.01 mol%, based on the whole monomer constituting the aliphatic polyester resin (100 mol%). The upper limit is usually 1 mol% or less, preferably 0.5 mol% or less.

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

  The aliphatic polyester resin (A ′) can be produced by a known method. For example, a general method of melt polymerization in which an esterification reaction and / or a transesterification reaction between the aliphatic dicarboxylic acid component and the aliphatic diol component is performed, followed by 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. A carboxylate, an alkoxy salt, an organic sulfonate, a compound containing an organic group such as a β-diketonate complex, an inorganic compound such as an oxide of a metal or a halide, or a mixture 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. The reaction temperature at this time has a lower limit of usually 150 ° C. or higher, preferably 180 ° C. or higher, and an upper limit of 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 ′), a known vertical or horizontal stirred tank reactor can be used. For example, melt polymerization is performed 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 connected as a reduced pressure polycondensation reactor. The method of using the stirred tank reactor equipped with the exhaust pipe for pressure reduction is 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 molar ratio of the diol component and the dicarboxylic acid component for obtaining the aliphatic polyester resin (A ′) having the desired degree of polymerization is different depending on the purpose and the type of raw material, but the acid component The amount of the diol component relative to 1 mol is usually lower limit of 0.8 mol or more, preferably 0.9 mol or more, and upper limit is usually 1.5 mol or less, preferably 1.3 mol or less, particularly preferably 1 .2 mol or less. Moreover, you may introduce | transduce a urethane bond, an amide bond, a carbonate bond, an ether bond, etc. in the aliphatic polyester-type resin (A) in the range which does not affect biodegradability.

  The melt flow rate (MFR) of the aliphatic polyester resin (A) used in the resin composition of the present invention is usually 0.1 g / 10 when measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K7210. Min. Or more, 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 upper limit of MFR is usually 100 g / 10 min or less, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and most preferably 10 g / 10 min or less.

  The content of the aliphatic polyester-based resin (A) in the resin composition of the present invention is usually 20% or more, preferably 30% or more, and more preferably, by mass ratio, based on the whole resin composition (100%). Is 40% or more, more preferably 50% or more, and the upper limit of the content is 94.9% or less, preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less. When there is too much content of aliphatic polyester-type resin (A), mechanical properties, such as tensile elongation, will fall and it is unpreferable in order to use it as various packaging materials. On the other hand, if the content of the aliphatic polyester resin (A) is too small, the moldability is deteriorated and the biodegradation rate is undesirably decreased.

<Aromatic aliphatic polyester resin (B)>
The resin composition of the present invention contains an aromatic aliphatic polyester resin (B) mainly composed of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and an aliphatic diol. In this case, the content of the aromatic dicarboxylic acid unit is preferably 10 mol% or more and 80 mol% or less based on the total amount of the aliphatic dicarboxylic acid unit and the aromatic dicarboxylic acid unit (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. 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. Further, aromatic dicarboxylic acids in which a part of the aromatic ring is substituted with a sulfonate are also included.

  Two or more kinds of the aliphatic dicarboxylic acid component, the aliphatic diol component, and the aromatic dicarboxylic acid component can be used. The aromatic aliphatic polyester resin (B) may also contain a small amount of aliphatic oxycarboxylic acid units as long as the properties are not impaired. The aromatic aliphatic polyester resin (B) is preferably polybutylene terephthalate adipate and / or polybutylene terephthalate succinate resin.

  The melt flow rate (MFR) of the aromatic aliphatic polyester resin (B) used in the resin composition of the present invention is usually 1.0 g / 10 min or more when measured at 190 ° C. and a load of 2.16 kg, preferably Is 2.0 g / 10 min or more, most preferably 3.0 g / 10 min or more, and the upper limit is usually 6.0 g / 10 min or less, preferably 5.0 g / 10 min or less, more preferably 4.0 g / min. 10 minutes or less. If the MFR is smaller than 1.0 g / 10 min, the fluidity at the time of molding is poor, which is not preferable. On the other hand, if the MFR is larger than 6.0 g / 10 min, the mechanical properties of the film or the molded product are lowered.

  The content of the aromatic aliphatic polyester resin (B) is a mass ratio based on the whole resin composition (100%), and is usually 5% or more, preferably 10% or more, more preferably 20% or more, The upper limit is 60% or less, preferably 50% or less, and more preferably 40%. If the content of the aromatic aliphatic polyester-based resin (B) is too large, the stiffness of the film is insufficient, and it is not preferable because the thickness of the film needs to be increased for use as various packaging materials. In addition, the biodegradability is decreased for applications requiring biodegradability, which is not preferable. On the other hand, if the content of the aromatic aliphatic polyester resin (B) is too small, the tensile elongation and tear strength are insufficient, which is not preferable.

<Compatibilizer (C)>
The compatibilizer (C) having a polar group and / or an aromatic group is added to the resin composition of the present invention. A compatibilizing agent is an additive that improves compatibility when mixing incompatible dissimilar resins. The compatibilizer (C) used in the present invention has a polar group and / or an aromatic group, and has a function of promoting compatibilization of two or more components of an incompatible resin, or an improved dispersion state. If it has the function to perform, it will not be restrict | limited in particular.

  Specific examples of the compatibilizer (C) include thermoplastic block copolymers, graft copolymers, random copolymers, and homopolymers, but block copolymers and graft copolymers may be used. preferable. The basic skeleton of the polymer is polystyrene, polyethylene, polypropylene, polymethyl methacrylate, polymethyl acrylate, polyvinyl chloride, ethylene propylene rubber, polyamide, EPDM, PPE, acrylonitrile styrene rubber, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyester Elastomer, SEBS, SBS, SIS, polysiloxane, etc. are mentioned, and these blocks, grafts, random copolymers, multiblock copolymers, and polymers modified with polar groups or aromatic groups in these basic skeletons are preferred. .

  Specific examples of polar groups include acid anhydride groups, epoxy groups, glycidyl groups, ester groups, ether groups, carbonyl groups, carboxyl groups, hydroxyl groups, amide groups, amino groups, cyano groups, isocyanate groups, carbodiimide groups, and oxazoline groups. Etc. Among these, an ester group, an epoxy group, and an acid anhydride group are preferable, and an ester group and a maleic anhydride group are particularly preferable. Examples of the aromatic group include phenyl group, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, naphthyl group, carsol group and alkyl groups thereof, halogen, nitro group, hydroxy group And substituted with sulfonic acid, preferably phenyl group, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, more preferably 1,4-phenylene group and It is a phenyl group.

  Specific examples of the compatibilizer having these polar groups and aromatic groups include SEBS, maleic anhydride-modified SEBS, ethylene-glycidyl methacrylate copolymer, EPDM-styrene / acrylonitrile graft copolymer and its maleic anhydride-modified. , Polyolefin elastomer-polystyrene graft copolymer, polyolefin elastomer-polystyrene acrylonitrile graft copolymer, vinyl acetate-styrene copolymer, ethylene-methacrylic acid copolymer, maleic anhydride modified polyolefin, vinyl acetate-EPDM- Polyolefin copolymer, polyethylene-polymethacrylate copolymer, polyethylene-polyether copolymer, polyether polyetheramide block copolymer, glycidyl group-containing copolyester, fat Aromatic polyester-aromatic aliphatic polyester biblock copolymer, aliphatic polyester-aromatic aliphatic polyester ternary block copolymer, aliphatic polyester-aromatic aliphatic polyester multiblock copolymer, aliphatic polyester- Aromatic aliphatic polyester graft copolymers may be mentioned. Among these, SEBS, maleic anhydride-modified SEBS, ethylene-glycidyl methacrylate copolymer, polyethylene-polymethacrylate copolymer, glycidyl group-containing copolyester, aliphatic polyester-aromatic aliphatic polyester binary block copolymer Coalesced, aliphatic polyester-aromatic aliphatic polyester ternary block copolymer, aliphatic polyester-aromatic aliphatic polyester multiblock copolymer, aliphatic polyester-aromatic aliphatic polyester graft copolymer, Further preferred specific examples include SEBS, maleic anhydride-modified SEBS, glycidyl group-containing copolyester, aliphatic polyester-aromatic aliphatic polyester binary block copolymer, aliphatic polyester-aromatic aliphatic polyester multi Lock copolymer, aliphatic polyester - and an aromatic aliphatic polyester graft copolymer. The most preferred compatibilizer is an aliphatic polyester-aromatic aliphatic polyester block copolymer and an aliphatic polyester-aromatic aliphatic polyester graft copolymer.

  The method for synthesizing the aliphatic polyester-aromatic aliphatic polyester graft copolymer is not particularly limited, and examples thereof include a method in which an aliphatic polyester and an aromatic aliphatic polyester are melt-kneaded together with an organic peroxide. As a method for synthesizing an aliphatic polyester-aromatic aliphatic polyester block copolymer, a method in which the ends of the aliphatic polyester and the aromatic aliphatic polyester are bonded to each other with diisocyanate, polyfunctional carbodiimide, or the like, or an ester exchange reaction is appropriately performed. Examples thereof include a method for producing a multiblock copolymer by exchanging. Examples of the reaction include solution reaction, melting reaction, and a method of reacting at the time of kneading.

  The content of the compatibilizing agent (C) in the resin composition of the present invention is usually 0.1% or more, preferably 0.5% or more, in mass ratio, based on the whole resin composition (100%). More preferably, it is 1% or more, more preferably 2% or more, and the upper limit of the content is 40% or less, preferably 20% or less, more preferably 10% or less, and further preferably 5% or less. If the content of the compatibilizing agent (C) is too large, the mechanical properties deteriorate, which is not preferable. On the other hand, if the content of the compatibilizing agent (C) is too small, the effect of improving the compatibilization becomes insufficient, which is not preferable.

<Organic additive>
You may add an organic additive to the resin composition of this invention by the mass ratio of 40% or less with respect to the whole resin composition as needed. Specific examples of organic additives include carbodiimide compounds, diisocyanate compounds, oxazoline compounds, epoxy compounds, acid anhydrides, starch, modified starch, pregelatinized starch, rice flour, pulp, chitin / chitosan, coconut shell powder, wood flour, Bamboo powder, bark powder, natural fiber, powders such as kenaf and persimmon etc. are mentioned. These may be used alone or in combination of two or more.

  Preferred examples of the organic additive include a carbodiimide compound, a diisocyanate compound, an oxazoline compound, an epoxy compound, and an acid anhydride, and more preferably a carbodiimide compound and a diisocyanate compound.

  The addition amount of the organic additive is usually 0.001% or more, preferably 0.01% or more, more preferably 0.05% or more, and further preferably 0.1% by mass ratio with respect to the entire resin composition. That's it. The upper limit of the addition amount is usually 40% or less, preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, and most preferably 1% or less. If the amount added is less than 0.001%, the expected effect cannot be obtained. On the other hand, if the addition amount exceeds 40%, the moldability of the resin composition is deteriorated, and the mechanical properties and heat resistance of the resin composition molded article are also unfavorable.

<Other additives>
Furthermore, conventionally well-known various additives can be mix | blended with the resin composition of this invention. 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 wetting improvers, incineration aids, pigments, lubricants, dispersion aids and various surfactants, slip agents, hydrolysis inhibitors, freshness-preserving agents, antibacterial agents, inorganic fillers and the like. These may be used alone or in combination of two or more. Among these, it is particularly preferable to add a slip agent and an antiblocking agent.

  Examples of the anti-blocking agent include C6-C30 saturated fatty acid amide, saturated fatty acid bisamide, methylol amide, ethanol amide, natural silica, synthetic silica, synthetic zeolite, talc and the like.

  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.

  Antioxidants include BHT, hindered phenol antioxidants such as 2,2′-methylenebis (4-methyl-6-tert-butylphenol), tridecyl phosphite, diphenyldecyl phosphite, tetrakis (2,4 -Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester Phosphorous-based antioxidants such as phosphorous acid, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3-hydroxy-5,7-di-tert-butyl-furan-2-one, Lactones such as xylene reactive organisms, sulfur such as dilauryl thiodipropionate, distearyl thiodipropionate An antioxidant and a mixture of two or more thereof can be exemplified. Of these, hindered phenolic antioxidants are preferably used.

  As the UV absorber, among the UV absorbers such as benzophenone, benzotriazole, salicylic acid, and cyanoacrylate, a benzotriazole UV absorber is preferable. Specifically, 2- [2-hydroxy-3 , 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol. It is done.

  Specific examples of the light-proofing agent include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-Butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate is mentioned.

  Specifically, an ester surfactant of a saturated or unsaturated aliphatic carboxylic acid having 4 to 20 carbon atoms and a polyhydric alcohol is preferably used as the antifogging agent. The antifogging agent may be kneaded into the resin in advance, or may be applied to the surface of the molded product after molding.

  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.

<Method for producing resin composition>
The aliphatic polyester-based resin (A), the aromatic aliphatic polyester-based resin (B), the compatibilizing agent (C), etc., which are the raw materials of the resin composition described above, are made into a resin composition by being melt-mixed. .

  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. The above-mentioned various additives, organic fillers and the like can be added at any stage. At this time, for the purpose of uniformly dispersing various additives and the like, a blending oil or the like can also be used.

  In the present invention, the compatibilizing agent (C) is melt-kneaded with the aliphatic polyester resin (A) and / or the aromatic aliphatic polyester resin (B) in advance before molding the resin composition. Is preferred. The compatibilizer (C) may be added during the preparation of the resin composition as long as it is before molding, or one of the aliphatic polyester resin (A) and the aromatic aliphatic polyester resin (B). It may be kneaded into one or two kinds of polyesters and mixed with all the components of the resin composition by dry blending with other components at the time of preparing the resin composition. Alternatively, a master batch of a high-concentration compatibilizer (C) is prepared with the aliphatic polyester resin (A) and / or the aromatic aliphatic polyester resin (B), and the compatibilizer (C ) May be diluted by dry blending the aliphatic polyester-based resin (A) and / or the aromatic aliphatic polyester-based resin (B) so that the concentration becomes a predetermined concentration.

  The temperature at which the compatibilizer (C) and the aliphatic polyester resin (A) and / or the aromatic aliphatic polyester resin (B) are melt kneaded depends on the temperature of the resin used, but at least the resin The temperature is preferably higher than the temperature at which the composition molded article is molded.

  In mixing and kneading the resin, 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. As the kneader, a batch kneader such as a roll or an internal mixer, a single-stage or two-stage continuous kneader, a twin screw extruder, a single screw extruder, or the like can be used.

<Resin composition and molded resin composition>
The resin composition of the present invention can be used for molding by various molding methods applied to general-purpose plastics. The molding methods include, for example, compression molding (compression molding, laminate molding, stampable molding), injection molding, extrusion molding and coextrusion molding (film molding by inflation method or T-die method, laminate molding, pipe molding, electric wire / cable molding. , Profile molding), hollow molding (various blow molding), calender 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 thereof 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 these, extrusion molding, injection molding, foam molding, and hollow molding are preferably applied. The specific shape of the resin composition molded body is preferably applied to films, containers and fibers.

  Also, imparting chemical functions, electrical functions, magnetic functions, mechanical functions, friction / abrasion / lubricating functions, optical functions, thermal functions, biocompatibility and other surface functions to the resin composition molded body For the purpose, secondary processing can be appropriately performed. 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.

  The resin composition of the present invention is excellent in moldability, and a molded body formed from the resin composition has excellent surface characteristics and mechanical characteristics. For this reason, the resin composition molded body containing the resin composition of the present invention as a main component is a packaging material or agricultural material for packaging various foods, medicines, miscellaneous products, etc. It is suitably used in a wide range of applications such as building materials. Specific applications include injection molded products (for example, fresh food trays, fast food containers, outdoor leisure products, etc.), extruded products (films, for example, 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, Foams, shopping bags, garbage bags, compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, sanitary cover stock materials, cold storage boxes, cushioning films, multifilaments, synthetic paper, etc., surgery It can also be suitably used as a medical material such as a thread, suture, artificial bone, artificial skin, DDS such as 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. Also, packaging materials such as packaging films, bags, trays, bottles, cushioning foams, fish boxes, etc., and agricultural materials such as mulching films, tunnel films, house films, sun covers, grass protection sheets , Cocoon sheet, germination sheet, vegetation mat, nursery bed, flower pot, etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example at all unless the summary is exceeded. In addition, the physical property and the measuring method of evaluation items, and the types of resins employed in the following examples are as follows.

<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 tension test based on JISK6781.

<Measuring method of melt flow rate>
MFR (g / 10 min): Measured at 190 ° C. under a load of 2.16 Kg according to JIS K7210.

<Use resin>
Aliphatic polyester resin (A): GSPla (grade name: AZ91TN) manufactured by Mitsubishi Chemical Corporation (PBS (polybutylene succinate) resin; MFR = 4.5)
Aliphatic polyester resin (A): GSPla (grade name: AD92WN) manufactured by Mitsubishi Chemical Corporation (PBSA resin; MFR = 4.7)
Aromatic aliphatic polyester-based resin (B): Ecoflex (PBAT (polybutylene terephthalate adipate) -based resin; MFR = 3.3) manufactured by BASF

(Manufacture of resin composition)
Aliphatic polyester-based resin (A), aromatic aliphatic polyester-based resin (B), and compatibilizer (C) are used in the types and proportions shown in Table 1 and kneaded at 190 ° C. with a 30 mmΦ twin-screw extruder. And the pellet of Examples 1-5 and Comparative Examples 1-3 was created.

(Inflation film molding)
The obtained resin composition pellets were dried at 70 ° C. for 10 hours under a nitrogen flow, and then blown with a blow ratio of 2.5, a folding diameter of 300 mm, and a molding temperature of 160 using an inflation molding machine (type E30SP manufactured by Engineering Plastics Industries Co., Ltd.). Films (Examples 1 to 5 and Comparative Examples 1 to 3) having thicknesses shown in Table 1 were molded at ° C. The physical property measurement results are shown in Table 1.

  The resin compositions (Examples 1 to 5) of the present invention had good evaluation results for all mechanical properties. Moreover, in Example 1- Example 5, film moldability was favorable and all the surfaces of the obtained film were smooth. On the other hand, Comparative Examples 1 to 3 in which the compatibilizing agent (C) defined in the present invention was not included were inferior particularly in terms of tear strength as compared with films having the same thickness.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. However, it can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and the resin composition accompanying such a change is also included in the technical scope of the present invention. Must be understood.

Claims (4)

A resin composition containing an aliphatic polyester-based resin (A), an aromatic aliphatic polyester-based resin (B), and a compatibilizer (C) having an epoxy group and / or an aromatic group is included as a main component. It is a film , Comprising: The mass ratio of each component with respect to the said whole resin composition is said aliphatic polyester-type resin (A) 20-94.9%, said aromatic aliphatic polyester-type resin (B) 5-60%, A film comprising 0.1 to 40% of a compatibilizer (C) having the epoxy group and / or aromatic group. The film according to claim 1, wherein the compatibilizer (C) is a block copolymer and / or a graft copolymer. The aliphatic polyester-based resin (A) is mainly composed of an aliphatic dicarboxylic acid and an aliphatic diol, and includes “trifunctional or higher aliphatic polyhydric alcohol” and “trifunctional or higher aliphatic polyvalent carboxylic acid”. At least one compound selected from “acid or acid anhydride thereof” and “trifunctional or higher aliphatic polyvalent oxycarboxylic acid” with respect to the entire raw material constituting the aliphatic polyester resin (A), The film according to claim 1 or 2, which is a resin copolymerized in an amount of 0.0001 to 1 mol%. The said aromatic aliphatic polyester resin (B) is polybutylene terephthalate adipate and / or polybutylene terephthalate succinate, The film of any one of Claims 1-3 characterized by the above-mentioned.