JP5218724B2 - Film containing polyester resin composition - Google Patents

Description

  The present invention relates to a polyester-containing film having excellent mechanical properties, and further has degradability in a natural environment, excellent mechanical properties, moldability, surface properties when formed into a molded body, etc. Relates to an excellent film.

  Conventionally, paper, plastic film, aluminum foil, and the like have been used in a wide range of applications such as liquids and granules for various foods, medicines, miscellaneous goods, solid packaging materials, agricultural materials, and building materials. In particular, plastic films are excellent in strength, water resistance, moldability, transparency, cost, etc., and are used in many applications as bags and containers. Examples of plastics currently used for these applications include polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. However, the film made of the above plastic does not biodegrade or hydrolyze in the natural environment, or the degradation rate is extremely slow, so if it is buried in the soil after use or dumped May damage the landscape. Moreover, even when incinerated, there are problems such as generation of harmful gases and damage to the incinerator.

  Therefore, many studies using biodegradable materials have been made as means for solving the above problems. Typical examples of biodegradable materials include aliphatic polyesters such as polylactic acid, polybutylene succinate and polybutylene succinate adipate, aromatic aliphatic copolymer polyester resins such as polybutylene adipate terephthalate, and sulfonated aromatics. Aromatic aliphatic copolyesters containing aliphatic groups are known.

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

  On the other hand, an aromatic aliphatic copolyester resin having an aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit and an aliphatic diol unit such as polybutylene adipate terephthalate (Patent Document 2), and an aromatic containing a sulfonic acid metal salt An aliphatic copolyester resin (Patent Document 3) is disclosed. In order to develop sufficient biodegradability, it is necessary that aliphatic units exist between the aromatic units, but such materials have a low crystallization rate and have a problem in moldability. There is. In addition, since the surface of the molded product is sticky, the opening characteristics of the inflation film are poor, but when an antiblocking agent or the like is blended, an opaque feeling is produced. In addition, this material is sufficiently flexible, but has a low tensile strength, resulting in a so-called waistless film.

  As a technique for solving these problems, a resin composition comprising a biodegradable polymer containing an aromatic dicarboxylic acid as a constituent unit and an aliphatic polyester and a molded article obtained from the composition are disclosed (see Patent Document 4). ). However, since the aliphatic polyester used in this example is polyethylene succinate, the crystallization rate is slow and the moldability may be poor. In addition, for a biodegradable polymer containing an aromatic carboxylic acid as an essential constituent unit, reducing the aromatic dicarboxylic acid component leads to a decrease in melting point, etc. For this reason, a polymer into which a considerable amount of an aromatic dicarboxylic acid component is introduced is used in spite of sacrificing biodegradability.

JP-A-8-239461 Special table 2001-500907 JP 2004-331967 A JP 2005-015606 A

  The present invention has been made in view of the above-described background art, and its problem is to obtain a film containing a polyester resin having excellent mechanical properties, and further, it has degradability in a natural environment and has moldability. Another object is to obtain a film containing a polyester resin having excellent surface properties when formed into a molded body.

  As a result of repeated earnest studies to solve the above-mentioned problems, the present inventors have conducted earnest studies on aliphatic polyesters having excellent crystallinity and moldability and aromatic aliphatic copolymer polyesters. The inventors have found that a polyester-based resin composition that gives a film having both biodegradability and mechanical properties can be obtained by using a specific composition, and the present invention has been completed.

That is, the present invention
A film having a resin composition containing an aliphatic polyester (A) and an aromatic aliphatic polyester (B) comprising an aliphatic diol unit and an aliphatic dicarboxylic acid unit;
The content mass ratio (a / b) of the aliphatic polyester (A) and the aromatic aliphatic polyester (B) is in the range of 10/90 to 90/10,
The tear strength is 5 (N / mm) or more, and
The film has a tensile elongation at break of 300% or more, and contains 5 to 60 parts by mass of starch with respect to 100 parts by mass of the resin composition.

The present invention also provides:
The above composition is
Aliphatic polyester (A), and
It contains an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, a chain aliphatic and / or alicyclic diol unit, and the ratio of the aromatic dicarboxylic acid to the entire dicarboxylic acid is 40 mol% to 60 mol%. Aromatic aliphatic polyester (B) and / or
It contains an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, a chain aliphatic and / or alicyclic diol unit, and the ratio of the aromatic dicarboxylic acid to the whole dicarboxylic acid is 70 mol% to 90 mol%. An aromatic aliphatic polyester (C),
The mass ratio (a / b) of the aliphatic polyester (A) and the aromatic aliphatic polyester (B) is in the range of 10/90 to 90/10, and
Content ratio by mass of the aromatic aliphatic polyester (C) to the “total of the aliphatic polyester (A), the aromatic aliphatic polyester (B), and the aromatic aliphatic polyester (C)” (C / (a + b + c)) provides said film whose range is 0-0.5.

The present invention also provides:
The aromatic aliphatic polyester (C) provides the above film having an aromatic dicarboxylic acid unit in which a part of the aromatic dicarboxylic acid unit contained therein is sulfonated.

  According to the present invention, by mixing an aliphatic polyester and an aromatic aliphatic polyester having a specific structure at a specific ratio, it has excellent mechanical properties, has degradability in a natural environment, and has moldability. In addition, a film having excellent surface properties when formed into a molded body can be provided.

  Hereinafter, the present invention will be described. However, the present invention is not limited to the specific embodiments described below, and includes modifications that are arbitrarily modified within the technical scope of the present invention.

<Aliphatic polyester (A)>
In the present invention, the aliphatic polyester (A) refers to a polyester having substantially no aromatic ring in the molecule. Specifically, the aliphatic polyester (A) is represented by, for example, a chain aliphatic and / or alicyclic diol unit represented by the following formula (1), and the following formula (2). A chain aliphatic and / or alicyclic dicarboxylic acid unit.
—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, and is not limited to one type when copolymerized. ]
^-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, and is not limited to one type when copolymerized. ]

  In the formulas (1) and (2), “and” in the “divalent chain aliphatic hydrocarbon group and / or divalent alicyclic hydrocarbon group” means 2 in one molecule of the constituent component. This means that both a valent chain aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group may be contained. 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 3 to 10 carbon atoms is preferable, and an aliphatic diol component having 4 to 6 carbon atoms is particularly preferable. Specifically, for example, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like can be mentioned, among which 1,4-butanediol is particularly preferable. Two or more types of aliphatic diol components can be used.

  The aliphatic dicarboxylic acid component that gives 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 preferable. Particularly preferred. Specific examples of the aliphatic dicarboxylic acid component include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like, and succinic acid or adipic acid is particularly preferable. Two or more types of aliphatic dicarboxylic acid components can be used.

  Furthermore, the aliphatic polyester (A) 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, for example, lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, and 2-hydroxy3. , 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 exist in these, any of D-form, L-form and racemic form may be sufficient, and a form may be a solid, a 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 lower limit of the amount of the aliphatic oxycarboxylic acid is usually 0 mol% or more, preferably 0.01 mol% or more, and the upper limit is usually 30 in all the components constituting the aliphatic polyester (A). The mol% or less, preferably 20 mol% or less.

  In addition, the aliphatic polyester (A) of the present invention is composed of “a trifunctional or higher aliphatic polyhydric alcohol”, “a trifunctional or higher aliphatic polyvalent carboxylic acid or acid anhydride thereof” or “a trifunctional or higher functional fatty acid”. It is preferable to copolymerize the “aromatic polyoxycarboxylic acid” because the melt viscosity of the resulting aliphatic polyester (A) can be increased.

  Specific examples of the trifunctional aliphatic polyhydric alcohol include trimethylolpropane and glycerin, and 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, and specific examples of the tetrafunctional polyvalent carboxylic acid or its acid anhydride include: Examples include cyclopentanetetracarboxylic acid or acid anhydrides thereof. These may be used alone or in combination of two or more.

  In addition, the trifunctional aliphatic oxycarboxylic acid component 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 component 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. It is divided into a type that shares a group in the same molecule, and (iii) a type that shares three hydroxyl groups and one carboxyl group 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 generally 0 mol% or more, preferably 0.01 mol% or more, and the upper limit is the total component constituting the aliphatic polyester (A). Usually, it is 5 mol% or less, preferably 2.5 mol% or less.

  The aliphatic polyester (A) used in the present invention 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, Although it can manufacture also by the well-known solution heating dehydration condensation method using a solvent, the method of manufacturing polyester by melt polymerization performed in the absence of a solvent from a viewpoint of economical efficiency or the simplicity of a manufacturing process 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 14 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-containing salt, 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 described above, 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, the catalyst is preferably a compound that is liquid at the time of polymerization or that dissolves in the ester low polymer or the polyester because the polymerization rate is increased when the catalyst is melted or dissolved at the time of polymerization.

  The amount of catalyst added in the case of using a metal compound as the polymerization catalyst is such that 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, as the amount of metal relative to the produced polyester. Below, more preferably 250 ppm or less, particularly preferably 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, but 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.

  In the present invention, a known vertical or horizontal stirred tank reactor can be used as a reaction apparatus for producing polyester. 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 used as the reduced pressure polycondensation reactor. A method of using a stirred tank reactor equipped with a evacuation 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 molar ratio of the diol component and the dicarboxylic acid component for obtaining a polyester having a desired degree of polymerization differs in a preferred range depending on the purpose and the type of raw material, but the amount of the diol component relative to 1 mol of the acid component is The lower limit is usually 0.8 mol or more, preferably 0.9 mol or more, and the upper limit is usually 1.5 mol or less, preferably 1.3 mol or less, particularly preferably 1.2 mol or less. Moreover, a urethane bond, an amide bond, a carbonate bond, an ether bond, or the like can be introduced as long as the biodegradability is not affected.

  The aliphatic polyester (A) used in the present invention has a sufficiently high crystallization rate, and the half-value width of the exothermic peak based on crystallization when cooled at 10 ° C./min in the differential scanning calorimeter measurement is Usually, it is 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 index (MFR) of the aliphatic polyester (A) used in the present invention, when measured at 190 ° C. and 2.16 kg, the lower limit is usually 0.1 g / 10 min or more, and the upper limit is usually It is 100 g / 10 min or less, preferably 50 g / 10 min or less, particularly preferably 30 g / 10 min or less.

  In the middle of the production method of the present invention or in the obtained polyester, various additives such as a heat stabilizer, an antioxidant, a crystal nucleating agent, a flame retardant, an antistatic agent, a release agent and the like can be used as long as the characteristics are not impaired. An ultraviolet absorber or the like may be added during polymerization.

<Aromatic aliphatic polyester (B)>
The aromatic aliphatic polyester (B) used in the present invention includes an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a chain aliphatic and / or alicyclic diol unit. The aromatic dicarboxylic acid unit content is 5 mol% or more and 60 mol% or less with respect to the total amount of the aliphatic dicarboxylic acid unit and the aromatic dicarboxylic acid unit. Hereinafter, “chain aliphatic and / or alicyclic” may be simply abbreviated as “aliphatic”. 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. Dimethanol etc. are mentioned, Among these, C2-C4 diol is preferable. Among these, ethylene glycol and 1,4-butanediol are more preferable, and 1,4-butanediol is particularly preferable.

  The dicarboxylic acid component that gives the carboxylic acid unit of the formula (4) is usually one having 2 to 10 carbon atoms. For example, specific examples of the aliphatic dicarboxylic acid component include succinic acid, adipic acid, suberic acid, Examples thereof include sebacic acid and dodecanedioic acid, among which 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, etc. Among them, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable. .

  In order to develop biodegradability in the aromatic aliphatic polyester (B) used in the present invention, it is necessary that an aliphatic chain exists between the aromatic rings. Therefore, the amount of the aromatic dicarboxylic acid unit in the aromatic aliphatic polyester (B) is 5 mol% or more based on the total amount of the aliphatic dicarboxylic acid unit and the aromatic dicarboxylic acid unit, preferably It is 30 mol% or more, more preferably 40 mol% or more, and particularly preferably 45 mol% or more. Moreover, about an upper limit, although 60 mol% or less is essential, 55 mol% or less is preferable. If this amount is too small, the effect of improving the mechanical strength such as tear strength may be lowered when a composition with the aliphatic polyester (A) is obtained. Moreover, when there is too much, biodegradability may become inadequate.

  Two or more types of aliphatic dicarboxylic acid components, aliphatic diol components, and aromatic dicarboxylic acid components can be used.

  Furthermore, the aliphatic aliphatic polyester (B) 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-hydroxy3,3 -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 exist in these, any of D-form, L-form and racemic form may be sufficient, and a form may be a solid, a 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 lower limit of the amount of the aliphatic oxycarboxylic acid is usually 0 mol% or more, preferably 0.01 mol% or more, and the upper limit is usually 30 in all the components constituting the aromatic aliphatic polyester (B). The mol% or less, preferably 20 mol% or less.

  The aromatic aliphatic polyester (B) can be produced by the same production method as the aliphatic polyester (A).

  When the melt flow index (MFR) of the aromatic aliphatic polyester (B) used in the present invention is measured at 190 ° C. and 2.16 kg, the lower limit is usually 0.1 g / 10 min or more, and the upper limit is usually It is 100 g / 10 min or less, preferably 50 g / 10 min or less, particularly preferably 30 g / 10 min or less.

  In the present invention, the content mass ratio (a / b) of the aliphatic polyester (A) and the aromatic aliphatic polyester (B) is preferably in the range of 10/90 to 90/10. A range of / 80 to 70/30 is particularly preferable. If the amount of the aromatic aliphatic polyester (B) is too small, the effect of improving the mechanical strength such as tear strength may be lowered. On the other hand, if the amount is too large, the surface of the molded product may become sticky, for example, the opening property of the inflation film may be deteriorated.

  The mass proportion of the aromatic aliphatic polyester (B) in the polyester resin composition is the sum of the aliphatic polyester (A), the aromatic aliphatic polyester (B), and the aromatic aliphatic polyester (C). The lower limit is 5 parts by mass or more, preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, and the upper limit is 90 parts by mass or less, preferably 80 parts by mass or less, particularly preferably 70 parts by mass with respect to 100 parts by mass. It is as follows. If this amount is too small, the effect of improving the mechanical strength such as tear strength tends to be low. On the other hand, if the amount is too large, the surface of the molded product becomes sticky, for example, the opening property of the inflation film tends to be deteriorated.

<Aromatic aliphatic polyester (C)>
The aromatic aliphatic polyester (C) used in the present invention includes an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, a chain aliphatic and / or alicyclic diol unit, and is aromatic. The ratio of dicarboxylic acid to the whole dicarboxylic acid is greater than 60 mol%. Hereinafter, “chain aliphatic and / or alicyclic” may be simply abbreviated as “aliphatic”.

Specifically, for example, it can be represented as a polyester containing constituent components represented by the following formulas (6) to (9).
—O—R ⁶ —O— (6)
[In the formula (6), R ⁶ represents a divalent chain aliphatic hydrocarbon group and / or a divalent alicyclic hydrocarbon group, and is not limited to one type when copolymerized. ]
_{^{-O- (R 7 -O) n -}} (7)
[In the formula (7), R ⁷ 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 ⁸ —CO— (8)
[In the formula (8), R ⁸ 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 ⁹ —CO— (9)
[In Formula (9), R ⁹ represents a divalent aromatic hydrocarbon group, and is not limited to one type when copolymerized. ]

  For example, the aliphatic diol unit represented by the above formula (6) has a carbon number of usually 2 or more and 10 or less, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like can be mentioned, and among these, a diol having 2 to 4 carbon atoms is preferable. Among these, ethylene glycol and 1,4-butanediol are more preferable, and ethylene glycol is particularly preferable.

  The diol unit represented by the above formula (7) contains an aliphatic ether unit. Specific examples include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, poly 1,3-propanediol, polytetramethylene glycol and the like, preferably polyethylene glycol, triethylene glycol, diethylene glycol and the like, more preferably Diethylene glycol or polyethylene glycol. n is preferably 1 to 1000, and more preferably 1 to 100.

  Further, the ratio of the aliphatic diol unit represented by the above formula (6) and the diol unit represented by the above formula (7) is preferably 80/20 to 100/0 in terms of molar ratio. 90/10 to 99/1 is preferred.

  The aliphatic dicarboxylic acid component giving the aliphatic dicarboxylic acid unit represented by the above formula (8) preferably has 2 or more and 10 or less carbon atoms. Specific examples thereof include succinic acid, glutaric acid, Adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like can be mentioned, among which succinic acid and glutaric acid are more preferable, and glutaric acid is particularly preferable.

  Examples of the aromatic dicarboxylic acid component that gives the aromatic dicarboxylic acid unit of the formula (9) include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. In addition, aromatic dicarboxylic acids in which a part of their aromatic rings are substituted with sulfonates can be mentioned.

That is, in the aromatic dicarboxylic acid unit R ⁹ represented by the above formula (9), a part of the aromatic ring may be substituted with a sulfonate. As the aromatic dicarboxylic acid component giving the aromatic dicarboxylic acid unit of the above formula (9), terephthalic acid, isophthalic acid or a sulfonic acid substitution product thereof is particularly preferable. Specific examples of the substituted sulfonic acid include, for example, 2-sulfoterephthalate, 2-sulfoisophthalate, 4-sulfoisophthalate, 5-sulfoisophthalate and the like. Isophthalate or 5-sulfoisophthalate is more preferable, and 5-sulfoisophthalate is particularly preferable. The salt is preferably an alkali metal salt, more preferably a potassium salt or a sodium salt, and particularly preferably a sodium salt.

The proportion of the aromatic dicarboxylic acid unit substituted with the sulfonic acid alkali salt in the total aromatic dicarboxylic acid unit represented by R ⁹ in the formula (9) is preferably 0.01 mol% or more and 20 mol% or less. It is more preferably 1 mol% or more and 10 mol% or less, and particularly preferably 0.5 mol% or more and 5 mol% or less. The ratio of the aromatic dicarboxylic acid substituted with the sulfonic acid alkali salt in the above formula (9) to the total dicarboxylic acid in the aromatic aliphatic polyester (C) of the present invention is 0.01 mol% or more and 20 The mol% or less is preferable, 0.1 mol% or more and 10 mol% or less is more preferable, and 0.5 mol% or more and 5 mol% or less is particularly preferable.

  In the aromatic aliphatic polyester (C), it is essential that the ratio of the aromatic dicarboxylic acid represented by the above formula (9) to the whole dicarboxylic acid ((8) + (9)) is larger than 60 mol%. However, it is preferably 70 to 90 mol%, particularly preferably 75 to 85 mol%.

  When the melt flow index (MFR) of the aromatic aliphatic polyester (C) used in the present invention is measured at 230 ° C. and 2.16 kg, the lower limit is usually 0.1 g / 10 min or more, and 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.

  Content ratio by mass of the aromatic aliphatic polyester (C) to the “total of the aliphatic polyester (A), the aromatic aliphatic polyester (B), and the aromatic aliphatic polyester (C)” (C / (a + b + c)) is preferably in the range of 0-0.5, more preferably in the range of 0.01-0.4, particularly preferably in the range of 0.05-0.35, and 0.1-0. A range of 3 is more preferred. If the amount of the aromatic aliphatic polyester (C) is too small, the effect of improving mechanical strength such as tear strength and tensile elongation at break may be lowered. On the other hand, if the amount is too large, tensile elongation at break may decrease, impact resistance may decrease, and biodegradability may decrease.

<Inorganic filler>
It is preferable to add an inorganic filler to the resin composition contained in the film of the present invention. Such inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, walla Stenite, calcined perlite, "silicates such as calcium silicate and sodium silicate", aluminum oxide, magnesium carbonate, "hydroxides such as calcium hydroxide", ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, sulfuric acid Barium etc. are mentioned. These may be used alone or in combination of two or more.

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

  Some inorganic fillers, such as calcium carbonate and limestone, have the properties of soil improvers. If a resin composition containing a large amount of these inorganic fillers is dumped in the soil, the resin composition However, after biodegradation, the inorganic filler remains and functions as a soil conditioner. In the case of applications such as agricultural materials and civil engineering materials that are dumped in the soil, it is the present invention that polyesters added with chemical fertilizers, soil conditioners, plant activators, etc. are used as molded articles. Will increase the usefulness of polyester.

<Organic filler>
Examples of organic fillers include raw starch, processed starch, pulp, chitin / chitosan, coconut shell powder, bamboo powder, bark powder, and powders such as kenaf and straw. These may be used alone or in combination of two or more. As for content of the organic filler in a resin composition, 60 mass% or less is preferable with respect to 100 mass parts of resin compositions.

  In the present invention, 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 to 60 parts by mass, more preferably 10 to 40 parts by mass, and more preferably 15 to 30 parts by mass with respect to 100 parts by mass of the resin composition. It is particularly preferable that it is contained. 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 hygroscopic property may be high and the product life may be shortened. When starch is contained, even if the aromatic aliphatic polyester (C) is not contained, there is an effect of improving mechanical strength such as tear strength and tensile elongation at break.

<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 and various surfactants, slip agents, antifogging agents, hydrolysis inhibitors, 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.

  The antifogging agent may be kneaded into the antifogging agent in advance, 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 and 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-t-butyl-4-hydroxyphenyl) -2-n-butyl-bis (1,2, 2,6,6-pentamethyl-4-piperidyl) malonate, 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butyl-bis (2,2,6,6-tetra Methyl-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'- Tramethyl-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-tetramethyl) -1,4-piperidyl) oxysucci , 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 Examples include 5-triazine condensates and N-methyl compounds thereof, polycondensates of succinic acid and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-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.

  The ultraviolet absorber that may be added to the film of the present invention is preferably a benzotriazole-based ultraviolet absorber among benzophenone-based, benzotriazole-based, salicylic acid-based, cyanoacrylate-based ultraviolet absorbers, 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.

  Antioxidants that may be added to the film 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-a, a ′, a ″-(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- Hydroxybe Ndyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, calcium diethylbis [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] 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) -6-methylphen L] ethyl ester phosphorous acid, phosphorus antioxidants such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3-hydroxy-5,7-di-tert-butyl-furan- Examples thereof include lactone antioxidants such as 2-one and xylene reactive organisms, sulfur antioxidants such as dilauryl thiodipropionate and 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-a, a ′, a ″-(mesitylene-2) , 4,6-triyl) tri-p-cresol).

  The addition amount of these additives is 0.001 mass%-10 mass% normally as content in the whole resin composition. The lower limit of the addition amount is preferably 0.01% by mass, more preferably 0.1% by mass. The upper limit of the addition amount is preferably 5% by mass, more preferably 3% by mass. 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.

  Examples of the organic diisocyanate that is a raw material for producing the polycarbodiimide compound include aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, aliphatic diisocyanates such as hexamethylene diisocyanate, 2,6-diisopropylphenyl diisocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4 ′ -Diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate Mixtures with isocyanates, aromatic diisocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, cyclohexane-1,4-diisocyanate Isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, alicyclic diisocyanates such as methylcyclohexane diisocyanate.

  When synthesizing these polycarbodiimide compounds, a desired degree of polymerization can be controlled by using an active hydrogen-containing compound capable of reacting with monoisocyanate or other terminal isocyanate groups. Compounds used for such purposes include monoisocyanate compounds such as phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, Hydroxyl group-containing compounds such as polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether, amino group-containing compounds such as diethylamine, dicyclohexylamine, β-naphthylamine and cyclohexylamine, carboxyl group-containing compounds such as succinic acid, benzoic acid and cyclohexane acid, ethyl mercaptan , Mercapto group-containing compounds such as allyl mercaptan and thiophenol, It can be exemplified fine various epoxy group-containing compound.

  In the present invention, it is preferable to use a polycarbodiimide compound, and the degree of polymerization of the lower limit 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.

As the carbodiimidization catalyst used in the decarboxylation condensation reaction of organic diisocyanate, organophosphorus compounds and organometallic compounds represented by the general formula M (OR) _n (where M is titanium, sodium, potassium, vanadium, tungsten, hafnium) , Zirconium, lead, manganese, nickel, calcium, barium or the like, R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and n can be a metal atom M. Is preferred). Among them, phospholene oxides are preferable for organic phosphorus compounds, and alcosides of titanium, hafnium, and zirconium are preferable because of their high activity.

  Specific examples of the phospholene oxides include 3-methyl-1-phenyl-2-phospholene-1-oxide, 3-methyl-1-ethyl-2-phospholene-1-oxide, and 1,3-dimethyl-2. -Phospholene-1-oxide, 1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide and their double bond isomers Can be illustrated. Of these, 3-methyl-1-phenyl-2-phospholene-1-oxide, which is easily available industrially, is particularly preferable.

  The carbodiimide compound can be used alone or as a mixture of a plurality of compounds. The blending amount of the carbodiimide compound to the polyester resin composition of the present invention is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, particularly preferably, the lower limit per 100 parts by mass of the total amount of the polyester resin composition. Is 0.1 parts by mass or more, and the upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, particularly preferably 3 parts by mass or less. If the blending amount is too small, the hydrolysis inhibiting effect tends to be insufficient, and if it is too large, the addition effect is saturated and an effect commensurate with the increase in the amount cannot be obtained.

  The carbodiimide compound may be added during the preparation of the composition to be described later, or one of the aliphatic polyester (A), the aromatic aliphatic polyester (B), or the aromatic aliphatic polyester (C). Alternatively, it may be kneaded and mixed with two kinds of polyesters and mixed with all the components of the resin composition by dry blending with other components during molding. Alternatively, an aliphatic polyester (A) and / or an aromatic aliphatic polyester (B) is used to prepare a master batch of a high concentration carbodiimide, and an aliphatic polyester ( A) and / or the aromatic aliphatic polyester (B) may be dry blended and diluted.

<Other ingredients>
In the film of the present invention, other biodegradable resins, such as polylactic acid, polycaprolactone, polyamide, polyvinyl alcohol, cellulose ester and the like, starch, cellulose, paper, wood powder, chitin, as long as the effects of the present invention are not inhibited. -Fine animal / plant substance powders such as 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.

  In the present invention, the preparation method of the resin composition containing the aliphatic polyester (A), the aromatic aliphatic polyester (B), and the aromatic aliphatic polyester (C) is not particularly limited. Examples thereof include a method in which chips are melt-mixed with the same extruder, a method in which the chips are melted in separate extruders, and then mixed. 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 composition of the aliphatic polyester (A), the aromatic aliphatic polyester (B), and the aromatic aliphatic polyester (C) is heated and melted, various additives, inorganic fillers, organic fillers, the above Examples include “other components”, a method of adding other polyesters, and the like. 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 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.).

  In the present invention, the composition is particularly preferably applied to an extrusion molding, an injection molded body, a foam molded body, a hollow molded body, and a specific shape as a film, a container and a fiber.

  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 this purpose, it is also possible to perform various purposeful secondary processing. 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 film of the present invention must have a tear strength of 5 (N / mm) or more. Preferably, it is 7 (N / mm) or more, particularly preferably 9 (N / mm) or more. “Tear strength” refers to “Elemendorf tear strength” of MD measured in accordance with JIS K7128. MD is a direction parallel to the flow of resin extruded from the molding machine.

  The film of the present invention must have a tensile elongation at break of 300% or more. Preferably it is 350 (%) or more, and particularly preferably 400 (%) or more. “Tensile elongation at break” was measured by a tensile test in accordance with JIS K6781. The tensile elongation at break of MD. MD is a direction parallel to the flow of resin extruded from the molding machine.

<Application>
The film of the present invention is excellent in moldability, surface properties and mechanical properties of molded articles while having degradability in a natural environment. It is suitably used in a wide range of applications such as materials, solid packaging materials, agricultural materials, and building materials. Specific applications include injection molded products (for example, fresh food trays, fast food containers, outdoor leisure products, etc.), extruded products (films, such as fishing lines, fishing nets, vegetation nets, water retaining sheets, etc.), hollow molding. Products (bottles, etc.), other agricultural films, coating materials, fertilizer coating materials, laminate films, plates, stretched sheets, monofilaments, non-woven fabrics, flat yarns, staples, crimped fibers, striped tape, Split yarn, composite fiber, blow bottle, foam, shopping bag, garbage bag, compost bag, cosmetic container, detergent container, bleach container, rope, binding material, sanitary cover stock material, cold box, cushion material film, multi Filament, synthetic paper, surgical thread, suture, artificial bone, artificial skin for medical use, Microcapsules etc. DDS of wound dressing and the like.

  In addition, 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. More preferably, 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 coverings, grass protections. Sheets, cocoon sheets, germination sheets, vegetation mats, nursery beds, flower pots and the like can be mentioned.

  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. “Tear strength” in the present invention indicates Elmendorf tear strength in “MD”.

<Measurement method of yield strength, breaking strength, tensile breaking elongation>
It measured by the tensile test based on JISK6781. The “tensile breaking elongation” in the present invention is the tensile breaking elongation at “MD”.

<Test method for biodegradation>
The molded film (thickness 35 μm) was buried in horticultural soil and left in a constant temperature and humidity chamber at 50 ° C. and 90% for 1 month, and then the taken out mass was measured to determine the mass reduction rate.

Synthesis example 1
[Synthesis of Aromatic Aliphatic Polyester (C)]
As the aromatic aliphatic polyester (C), an aromatic aliphatic polyester (PEGT resin) containing an aromatic group substituted with a sulfonate was synthesized as follows.
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer and a vacuum port, 81.5 parts by mass of dimethyl terephthalate, 9.25 parts by mass of glutaric acid, sodium dimethyl-5-sulfonate isophthalate 68 parts by mass, 43.7 parts by mass of ethylene glycol, 0.01 parts by mass of titanium tetrabutyrate, and 0.074 parts by mass of magnesium acetate tetrahydrate were charged. Nitrogen gas was introduced into the container while stirring the contents of the container, and the system was placed in a nitrogen atmosphere by vacuum replacement. Next, the temperature in the system was increased to 185 ° C. while stirring, and the reaction was carried out at this temperature for 45 minutes. Next, the temperature was raised to 220 ° C. over 1 hour and 30 minutes. Thereafter, the temperature was raised to 260 ° C. over 1 hour, and at the same time, the pressure was reduced to 0.07 × 10 ³ Pa or less over 1 hour and 30 minutes, and the polymerization was continued while maintaining the heated and reduced pressure state to obtain a predetermined viscosity. Then, the polymerization was terminated to obtain a copolymer.

Examples 1-17
In the mass ratio shown in Table 1, as an aliphatic polyester (A), a PBS resin (AZ91TN manufactured by Mitsubishi Chemical Corporation) and / or a PBSA resin (AD92WN manufactured by Mitsubishi Chemical Corporation), and an aromatic aliphatic polyester (B) PBAT resin (Ecoflex (registered trademark) manufactured by BASF), PEGT resin as aromatic aliphatic polyester (C) (aromatic fat containing aromatic group substituted with sulfonate obtained in Synthesis Example 1 above) Group polyester resin) and, if necessary, talc (Nihon Talc SG95) or starch (Nihon Corn Starch: Corn Starch Y-3P) was added and kneaded with a twin screw extruder.

  The kneaded pellets were dried at 70 ° C. under nitrogen for 10 hours. The dried pellets were subjected to inflation molding at 190 ° C. to obtain a film having a tough tear strength with a thickness of 35 μm. The evaluation results are shown in Table 1.

Comparative Examples 1-6
PBS resin (AZ91TN manufactured by Mitsubishi Chemical Co., Ltd.) and / or PBSA resin (AD92WN manufactured by Mitsubishi Chemical Co., Ltd.), PBAT resin (Ecoflex manufactured by BASF Co.), and PEGT resin (obtained in Synthesis Example 1) in the mass ratio shown in Table 1. The pellets of the aromatic aliphatic polyester resin containing an aromatic group substituted with a sulfonate were kneaded with a twin screw extruder.

  The kneaded pellets were dried at 70 ° C. under nitrogen for 10 hours. The dried pellets were subjected to inflation molding at 160 ° C. (200 ° C. only in Comparative Example 6) to obtain a film having a thickness of 35 μm. The evaluation results are shown in Table 1. The tear strength of the film was very weak.

  The film of the present invention is excellent in mechanical properties, biodegradability, moldability, and surface properties when formed into a molded body, so that it can be used for various foods, medicines, miscellaneous products, etc. It is widely used for construction materials, agricultural materials, building materials, etc.

Claims (5)

A film having a resin composition containing an aliphatic polyester (A) comprising an aliphatic diol unit and an aliphatic dicarboxylic acid unit and an aromatic aliphatic polyester (B), the aliphatic polyester (A) And the aromatic aliphatic polyester (B) content mass ratio (a / b) is in the range of 10/90 to 90/10, the tear strength is 5 (N / mm) or more, and the tensile elongation at break Is 300% or more, and 5 to 60 parts by mass of starch is contained with respect to 100 parts by mass of the resin composition. The resin composition is
Aliphatic polyester (A), and
It contains an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, a chain aliphatic and / or alicyclic diol unit, and the ratio of the aromatic dicarboxylic acid to the entire dicarboxylic acid is 40 mol% to 60 mol%. Aromatic aliphatic polyester (B) and / or
It contains an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, a chain aliphatic and / or alicyclic diol unit, and the ratio of the aromatic dicarboxylic acid to the whole dicarboxylic acid is 70 mol% to 90 mol%. An aromatic aliphatic polyester (C),
The mass ratio (a / b) of the aliphatic polyester (A) and the aromatic aliphatic polyester (B) is in the range of 10/90 to 90/10, and
Content ratio by mass of the aromatic aliphatic polyester (C) to the “total of the aliphatic polyester (A), the aromatic aliphatic polyester (B), and the aromatic aliphatic polyester (C)” The film of Claim 1 whose (c / (a + b + c)) is the range of 0-0.5.   The film according to claim 2, wherein the aromatic aliphatic polyester (C) has an aromatic dicarboxylic acid unit partially sulfonated.   The film according to any one of claims 1 to 3, wherein the aliphatic dicarboxylic acid unit is a chain aliphatic dicarboxylic acid unit.   The film according to any one of claims 1 to 4, wherein the inorganic filler is contained in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.