JP2006274252A - Aliphatic polyester having low branching degree and high molecular weight, molded article and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aliphatic polyester having low branching degree and high molecular weight and giving a molded article having biodegradability, practical heat-resistance, etc. <P>SOLUTION: The aliphatic polyester having low branching degree and high molecular weight has a molecular chain composed of an aliphatic dicarboxylic acid residue, an aliphatic diol residue and an aliphatic hydroxycarboxylic acid residue, wherein 100-75 mol% in 100 mol% of the aliphatic dicarboxylic acid residue is succinic acid residue, the molar ratio of the aliphatic hydroxycarboxylic acid residue to the sum of the aliphatic dicarboxylic acid residue and the aliphatic hydroxycarboxylic acid residue is 0-0.25, the weight-average molecular weight (Mw) is ≥180,000, the ratio (Mw/Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) is ≤2.7, and the content of the branching structure based on malic acid is ≤10×10<SP>-6</SP>mol/g. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention comprises an aliphatic dicarboxylic acid residue, an aliphatic diol residue, and an aliphatic hydroxycarboxylic acid residue added as necessary, and the specific ratio of the aliphatic dicarboxylic acid residues is a succinic acid residue. Yes, having a weight average molecular weight (Mw) of a specific value or more, a small ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and a low content of the branched structure of the specific structure TECHNICAL FIELD The present invention relates to a branched high molecular weight aliphatic polyester, a molded article thereof, and a film.

In recent years, aliphatic polyesters with high versatility have attracted attention as plastics that can be biodegraded in the natural environment, such as polylactic acid (PLA), poly (ε-caprolactone) (PCL), polybutylene succinate (PBS), Poly (butylene succinate-butylene adipate) copolymer (PBSA), poly (butylene succinate-ε-caprolactone) copolymer (PBSC), poly (butylene succinate-lactic acid) copolymer, poly (butylene succinate) -Butylene adipate-lactic acid) copolymer, polyethylene succinate (PES) and the like are on the market.
One of the uses of these biodegradable aliphatic polyesters is the film field for packaging, agriculture, food, etc., and high strength, heat resistance and biodegradability according to the use are required as basic performance. .

Among the above aliphatic polyesters, PLA is a stretched or highly crystallized film or molded product, which has a high melting point near 170 ° C. and high heat resistance, but it is hard or brittle. The composting equipment is necessary because it is low in degree and difficult to decompose in the soil.
On the other hand, PCL is a typical biodegradable plastic which is rich in flexibility and easily decomposes even in the soil, but its melting point is as low as about 60 ° C., and it is difficult to use it practically as it is. All other aliphatic polyesters are highly flexible crystalline polymers obtained using succinic acid and 1,4-butanediol or ethylene glycol as the main raw materials, and have good biodegradability in the soil. Accordingly, by adding other raw materials that can be polycondensed or polyadded, the melting point can be controlled to around 115 to 75 ° C., and practically sufficient heat resistance can be ensured.
These succinic aliphatic polyesters are disclosed in JP-A-4-189822 and JP-A-5-287043 (Patent Documents 1 and 2).

  In addition, many improvements have been reported for similar succinic aliphatic polyesters. For example, in JP-A-8-311181, an aliphatic dicarboxylic acid or an ester thereof, an aliphatic diol, a hydroxycarboxylic acid, a hydroxycarboxylic acid ester or a lactone is subjected to a polycondensation reaction in the presence of a catalyst to obtain a number average. A biodegradable high molecular weight aliphatic polyester copolymer having a molecular weight of 15,000 to 80,000 is disclosed (Patent Document 3). JP-A-9-272789 discloses an aliphatic polyester having a number average molecular weight of 1 to 300,000 by copolymerizing an aliphatic diol, an aliphatic dicarboxylic acid, and an aliphatic hydroxycarboxylic acid, and a number average molecular weight of 3 A resin composition obtained by melt blending 10,000 or more polylactic acids is disclosed (Patent Document 4).

  WO 02-44249 discloses a weight average molecular weight of 40 synthesized by a polycondensation reaction of a mixture of three components of an aliphatic diol, an aliphatic dicarboxylic acid, and an aliphatic hydroxycarboxylic acid or its anhydrous cyclic compound (lactones). It is disclosed that by using a high molecular weight aliphatic polyester copolymer of 1,000 or more and other biodegradable resins, the molecular weight stability at the time of molding of a film or the like is good and the molding is good (patent) Reference 5).

  Japanese Patent Application Laid-Open No. 2004-277715 uses succinic acid containing 0.25% by weight of malic acid, further added with adipic acid and lactic acid, and consists of succinic acid / adipic acid / lactic acid / malic acid-1,4-butanediol. It is disclosed that the crystallization temperature of an aliphatic polyester is 25 ° C. when no crystal nucleating agent is added, and increases from 25 to 43 ° C. when a crystal nucleating agent is added (Patent Document 6).

  However, each of the above technologies has a problem that the impact strength of the film is insufficient and it is easily broken when used as a shopping bag. On the other hand, it is well known that when the physical properties of a molded product are weak, stress concentrates there and is remarkably reduced, and it is important to keep the physical properties uniform.

JP-A-4-189822 (Claims, Examples) JP-A-5-287043 (Claims, Examples) JP-A-8-311181 (Claims, Examples) JP-A-9-272789 (Claims, Examples) WO 02-44249 (claim, final paragraph of invention disclosure, Table VII-1) JP 2004-277715 A ([0021], [Example])

A first object of the present invention is a biodegradable aliphatic polyester molded article having biodegradability and practical heat resistance, improved physical properties such as elastic modulus, ductility, impact resistance and the like, and less physical property variation. And a low branching high molecular weight aliphatic polyester that provides it.
In addition to the first object, a second object of the present invention is to provide a film that can be produced under a wide range of film forming conditions and has high impact resistance.

The present inventors have a branch point of a specific structure contained in an aliphatic polyester having an ester bond based on an aliphatic dicarboxylic acid residue, an aliphatic diol residue, and an aliphatic hydroxycarboxylic acid residue added as necessary. It was found that a low-branching high molecular weight aliphatic polyester was obtained by controlling the concentration of this to a specific value or less, and the first problem was solved, and the present invention was completed.
The present inventors have found that the second problem can be solved by forming a specific film using the low-branched high molecular weight aliphatic polyester, and have completed the present invention. .

That is, in the first aspect of the present invention, the molecular chain is substantially equimolar in the amount of the structural units represented by the following general formulas (1) and (2) (the structural units represented by (1) and (2)). ),
—CO—R ¹ —CO— (1)
(In the formula, R ¹ represents a C 1-12 divalent aliphatic group.)
—O—R ² —O— (2)
(Wherein R ² represents a divalent aliphatic group having 2 to 12 carbon atoms), and a structural unit represented by the following general formula (3) —CO—R ³ —O— (3)
(In the formula, R ³ represents a divalent aliphatic group having 1 to 10 carbon atoms.)
A low-branching high molecular weight aliphatic polyester consisting of
100-75 mol% of 100 mol% of the structural units represented by the general formula (1) is a succinic acid residue,
The molar fraction of the structural unit amount represented by the general formula (3) to the sum of the structural unit amounts represented by the general formulas (1) and (3) is 0 to 0.25,
The weight average molecular weight (Mw) is 180,000 or more,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.7 or less,
CH group by ¹ H-NMR measurement of a branched structure represented by the following formula (4):
—O—C (═O) —CH (O—C (═O) —) CH ₂ —C (═O) O— (4)
A low-branching high molecular weight aliphatic polyester having a content of 10 × 10 ⁻⁶ mol / g or less is provided.
A second aspect of the present invention provides the low-branched high molecular weight aliphatic polyester according to the first aspect of the present invention, which has an acid value of 2.0 mgKOH / g or less.
A third aspect of the present invention provides the low-branched high molecular weight aliphatic polyester according to the first or second aspect of the present invention, wherein the hydroxyl group terminal concentration by ¹ H-NMR measurement is 40 × 10 ⁻⁶ mol / g or less.
The fourth aspect of the present invention is the low branching high molecular weight according to any one of the first to third aspects of the present invention, wherein the ether bond concentration measured by ¹ H-NMR measurement is 7.0 × 10 ⁻⁶ mol / g or less. An aliphatic polyester is provided.
According to a fifth aspect of the present invention, the structural unit represented by the general formula (1) includes 100 to 75 mol% of succinic acid residues and the remaining 0 to 25 mol% of adipic acid residues. 4. The low-branching high molecular weight aliphatic polyester according to any one of 4 is provided.
A sixth aspect of the present invention is the structure according to any one of the first to fifth aspects of the present invention, wherein the structural unit represented by the general formula (2) is an ethylene glycol residue and / or a 1,4-butanediol residue. A low-branching high molecular weight aliphatic polyester is provided.
According to a seventh aspect of the present invention, the structural unit represented by the general formula (3) is composed of ε-caprolactone, 4-methyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone, 3,5,5-trimethyl. A book that is a residue based on at least one selected from the group consisting of -ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, enanthlactone, glycolic acid, lactic acid, and 3-hydroxybutyric acid The low branching high molecular weight aliphatic polyester according to any one of Items 1 to 6 of the invention is provided.
In the eighth aspect of the present invention, the molar fraction of the structural unit amount represented by the general formula (3) to the total amount of the structural units represented by the general formulas (1) and (3) is 0.04 to 0.25. The low branching high molecular weight aliphatic polyester according to any one of Items 1 to 7 of the present invention is provided.
According to the ninth aspect of the present invention, the low-branched high molecular weight aliphatic polyester comprises polybutylene succinate, poly (butylene succinate-butylene adipate) copolymer, poly (butylene succinate-ε-caprolactone) copolymer, poly The low of any one of 1-8 of this invention which is a (butylene succinate-lactic acid) copolymer, a poly (butylene succinate-butylene adipate-lactic acid) copolymer, and / or a polyethylene succinate. A branched high molecular weight aliphatic polyester is provided.
A tenth aspect of the present invention provides a low-branched high molecular weight aliphatic polyester molded article obtained by molding the low-branched high molecular weight aliphatic polyester according to any one of the first to ninth aspects of the present invention.
In the eleventh aspect of the present invention, the molding is extrusion molding, injection molding, compression molding, injection compression molding, transfer molding, cast molding, stampable molding, blow molding, stretched film molding, inflation film molding, laminate molding, calendar molding, The low branching high molecular weight aliphatic polyester molded article according to the tenth aspect of the present invention, which is foam molding, RIM molding, FRP molding, powder molding or paste molding.
According to the twelfth aspect of the present invention, an elastic deformation energy Ep (unit: J) up to a yield point in a strain-stress curve and a fracture after the yield point of a compression molded product having a thickness of 1.5 mm by a drop impact test based on ASTM D3763. The low branched high molecular weight aliphatic polyester molding according to the tenth or eleventh aspect of the present invention, wherein the total absorbed energy Eg + Ep (unit: J) is 10 J or more when the propagation energy Eg (unit: J) to the point is measured Provide goods.
A thirteenth aspect of the present invention provides the low-branched high molecular weight aliphatic polyester molded article according to the twelfth aspect of the present invention, wherein the propagation energy Eg is 5.5 J or more.
A fourteenth aspect of the present invention is a low-branching high molecular weight aliphatic polyester molded article according to any one of the tenth to thirteenth aspects of the present invention, wherein the film has a thickness of 5 μm to 0.5 mm and is not stretched or A low-branching high molecular weight aliphatic polyester film that is uniaxially or biaxially stretched is provided.
A fifteenth aspect of the present invention is the fourteenth aspect of the present invention, in which a falling ball impact test height H (d = thickness) using a sphere having a diameter of 19 mm and a weight of 28 g is 20 cm or more when converted to a film thickness of 20 μm. A low-branching high molecular weight aliphatic polyester film is provided.
A sixteenth aspect of the present invention is the fourteenth aspect of the present invention, in which the thermal shrinkage stress (SMD) in the MD direction is 0.4 MPa or less and the ratio SMD / STD to the thermal shrinkage stress (STD) in the TD direction is 10 or less. 15. A low branching high molecular weight aliphatic polyester film according to 15,
The seventeenth aspect of the present invention is the fourteenth to sixteenth aspect of the present invention in which the average value of elongation at break is 750% or more and the variation rate thereof is 15% or less by a high-speed tensile test in the TD direction (Daicel method). The low-branching high molecular weight aliphatic polyester film according to any one of the above is provided.
According to an eighteenth aspect of the present invention, any one of the fourteenth to seventeenth aspects of the present invention, wherein an average value of absorbed energy is 150 MPa or more and a variation rate is 50% or less by a Charpy impact test (Daicel method) in a TD direction of the film A low-branching high molecular weight aliphatic polyester film according to item 1 is provided.

According to the present invention, it becomes possible to easily obtain a low-branched high molecular weight aliphatic polyester industrially, and using it, it has biodegradability and practical heat resistance, and has an elastic modulus, ductility, A biodegradable aliphatic polyester molded article having improved physical properties such as impact resistance and little physical property variation can be obtained.
Further, according to the present invention, a film having higher impact resistance can be produced with high productivity at a wide range of film forming speeds and stretch ratios.

<Low branching high molecular weight aliphatic polyester>
The low-branching high molecular weight aliphatic polyester (a) according to the present invention (hereinafter sometimes simply referred to as “aliphatic polyester (a)”) has a molecular chain represented by the following general formulas (1) and (2). (The amount of the structural unit represented by (1) and (2) is substantially equimolar),
—CO—R ¹ —CO— (1)
(In the formula, R ¹ represents a C 1-12 divalent aliphatic group.)
—O—R ² —O— (2)
(In the formula, R ² represents a divalent aliphatic group having 2 to 12 carbon atoms.)
And a structural unit represented by the following general formula (3): —CO—R ³ —O— (3)
(In the formula, R ³ represents a divalent aliphatic group having 1 to 10 carbon atoms.)
A low-branching high molecular weight aliphatic polyester consisting of
Of 100 mol% of the aliphatic dicarboxylic acid residue represented by the general formula (1), 100 to 75 mol%, preferably 100 to 80%, more preferably 100 to 85 mol% are succinic acid residues,
The molar fraction of the structural unit amount represented by the general formula (3) to the sum of the structural unit amounts represented by the general formulas (1) and (3) is 0 to 0.25, particularly in (3) When the structural unit shown is included, it is preferably 0.04 to 0.25, more preferably 0.06 to 0.23, and particularly preferably 0.08 to 0.20.
The weight average molecular weight (Mw) is 180,000 or more, preferably 200,000 or more, more preferably 220,000 or more,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.7 or less, preferably 2.5 or less,
CH group by ¹ H-NMR measurement of a branched structure represented by the following formula (4):
—O—C (═O) —CH (O—C (═O) —) CH ₂ —C (═O) O— (4)
Is 10 × 10 ⁻⁶ mol / g or less, preferably 8.0 × 10 ⁻⁶ mol / g or less, and the ether bond concentration formed by the side reaction is 7.0 × 10 ⁻⁶ mol / g. It is a low-branching high molecular weight aliphatic polyester that is not more than g, and preferably not more than 3.0 × 10 ⁻⁶ mol / g.

The structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are usually connected adjacently to each other and the repeating unit (P) represented by the following general formula (6):
—CO—R ¹ —COO—R ² —O— (6)
(In the formula, R ¹ represents a divalent aliphatic group having 1 to 12 carbon atoms, and R ² represents a divalent aliphatic group having 2 to 12 carbon atoms.)
Form. In the repeating unit (P), the amount of the structural unit represented by the formulas (1) and (2) is equimolar.
In addition, the structural unit represented by the formula (1) may be included in, for example, a hydroxyl terminal or an ether bond portion generated by a side reaction other than in the repeating unit (P). Further, the structural unit represented by the formula (2) may be contained in, for example, an acid terminal portion other than in the repeating unit (P).
Therefore, a slight difference may occur between the amounts of the structural units represented by the formulas (1) and (2), but in the formulas (1) and (2) included in the aliphatic polyester (a) of the present invention. The difference in the amount of the structural unit shown is the ratio of the RM represented by the following formula (X):

RM value is usually in the range of 1.030 to 0.980, for example, 1.025 to 0.995. Therefore, the amount of the structural units represented by the formulas (1) and (2) contained in the aliphatic polyester (a) of the present invention is within a numerical range in which the molar fraction is sufficiently close, and is substantially equimolar. It is. When the aliphatic polyester (a) is a copolymer containing a structural unit represented by the formula (3), the repeating unit (Q) of the copolymer component is the same as the structural unit represented by the formula (3). The molar ratio of the repeating unit (P) represented by the formula (6) and the structural unit represented by the formula (3) (that is, the repeating unit (Q)) is the same as the structural unit represented by the formula (1) It is equal to the molar ratio of the structural unit represented by formula (3).

  In general, if the above numerical value is outside the range, the following problems are likely to occur. When the ratio of succinic acid residues is outside the above range, or when the molar fraction of the structural unit represented by the general formula (3) is outside the above range, the resulting aliphatic polyester has a melting point lower than 80 ° C. Become. Or when both of them are outside the above range at the same time, the melting point of the resulting aliphatic polyester becomes lower than 80 ° C., and the practical heat resistance cannot be maintained. Furthermore, it is preferable to select conditions so that the melting point of the resulting aliphatic polyester is 80 ° C. or higher even when both are within the above range.

Hereinafter, a case where a 1,4-butanediol residue is included as (2) will be described as a specific example. The aliphatic polyester (a) according to the present invention is composed of a succinic acid residue, 1,4-butanediol residue, and at least one other structural unit represented by formulas (1) to (3). In this case, the copolymer composition ratio (R) represented by the following formula (Y):
R = {[B] ・ [SA] + ([A] + [C]) ・ ([BG] + [B])} / {([SA] + [A] + [C]) ・ ([BG ] + [B])} (Y)
(In the formula, [SA] is an agglutinant whose denominator is the sum of the average number of moles of each of the structural units represented by formulas (1) to (3) (this sum may be abbreviated as (S) below). The molar concentration of acid units, [BG] is the molar concentration of 1,4-butanediol units with (S) as the denominator, and [A] to [C] are succinic acid residues and 1,4-butanediol residues. (Indicating the molar concentration of the structural units represented by the formulas (1) to (3) excluding) with (S) as the denominator.)
When the copolymer component is used, it is preferably 0.04 to 0.25, more preferably 0.06 to 0.23, and particularly preferably 0.08 to 0.00. It is preferable to select to be 20.

  When the molecular weight is small, specifically, when the weight average molecular weight (Mw) is smaller than the above numerical range, for example, when a film is formed, stretch moldability such as inflation molding or biaxial stretching is greatly reduced. For the purpose of improving stretch moldability, a technique has been disclosed such as introducing a branched structure into an aliphatic polyester to impart strain-hardening properties in a molten state. In this method, practical physical properties such as impact strength have been disclosed. It cannot be improved. On the other hand, if the molecular weight is sufficiently high, it is not necessary to have a branched structure in order to ensure moldability. Rather, if the content of the branched structure is larger than the above range, ductility, impact resistance, etc. It causes a decrease in practical physical properties due to an increase in the branched structure.

When the Mw / Mn ratio is too large, even if the weight average molecular weight is sufficiently large, the composition has a high content of the low molecular weight component, and the practical physical properties are deteriorated due to the influence of the low molecular weight component.
In general, in aliphatic polyester, the plastic deformation region consists of a cold-drawing region where the lamellar crystals are cleaved and stretched, and a region where the stretched molecular chain is unwound, and through these, the ductility is reduced. Demonstrates high impact strength. However, when there are many low molecular weight components as described above, or when the branching concentration is too high, these components may become stress concentration points, or the ductility due to cold drawing may not be sufficiently exhibited. The ductility cannot be exhibited and the impact strength is reduced.

  When the ether bond concentration is too much above the above range, the hue is deteriorated and the crystallinity is lowered, so that the melting point is lowered and the heat resistance is deteriorated. In addition, the biodegradability control is adversely affected.

  If the branching point concentration is more than the above range, the flow characteristics at the time of melt molding change, so the molding conditions must be changed, and the operation management becomes extremely complicated. Furthermore, a polymer containing many branch points significantly reduces the mechanical properties of the molded article, particularly the tensile elongation.

  Furthermore, when the acid value is outside the above range, the concentration of the acid component in the resin is high, and the molecular weight is likely to decrease due to hydrolysis, leading to a decrease in quality during molding.

The aliphatic polyester (a) according to the present invention has the above composition, and the low molecular weight aliphatic polyester (a ′) having a weight average molecular weight of 5,000 or more is 100 parts by weight of the low molecular weight aliphatic polyester (a ′). In contrast, 0.1 to 5 parts by weight of a bifunctional coupling agent (e) represented by the following general formula (7) is used so that the weight average molecular weight becomes the above high molecular weight. May be.
X ¹ -R ⁷ -X ² (7)
Wherein X ¹ and X ² are reactive groups capable of forming a covalent bond by acting with a hydroxyl group or a carboxyl group, R ⁷ represents a single bond, an aliphatic group or an aromatic group having 1 to 20 carbon atoms, ¹ and X ² may have the same chemical structure or may be different.)

  The aliphatic polyester (a) and the low molecular weight aliphatic polyester (a ′) according to the present invention are represented by the aliphatic dicarboxylic acids (A) that give the structural unit represented by the general formula (1) and the general formula (2). It is obtained by a polycondensation reaction using as raw materials an aliphatic diol (B) that gives a structural unit and a monomer component (C) that gives a structural unit represented by the general formula (3) that is added as necessary.

(A) Component Since 100 to 75 mol% of the structural unit represented by the formula (1) is a succinic acid residue, 100 to 75 mol% of the raw material (A) is succinic acid or a derivative thereof that can participate in polymerization ( A '). Examples of succinic acid or its derivative (A ′) that can participate in polymerization include succinic acid, succinic anhydride, dimethyl succinate, diethyl succinate and the like. Of these, succinic acid or succinic anhydride is preferably used from the viewpoint of industrial economy, and succinic acid is particularly preferably used.

Examples of the aliphatic dicarboxylic acids (A) that give an aliphatic dicarboxylic acid residue other than the succinic acid residue of the formula (1) include aliphatic dicarboxylic acids, anhydrides thereof, and mono- or diesters thereof. It is represented by the formula (1 ′).
R ⁴ —OCO—R ¹ —COO—R ⁵ (1 ′)
(In the formula, R ¹ represents a divalent aliphatic group having 1 to 12 carbon atoms, R ⁴ and R ⁵ represent a hydrogen atom, or an aliphatic group or aromatic group having 1 to 6 carbon atoms. R ⁴ and R ⁵ May be the same or different.)
The divalent aliphatic group represented by R ¹ is preferably a linear or cyclic alkylene group having 2 to 8 carbon atoms having 2 to 8 carbon atoms such as — (CH ₂ ) ₄ — and — (CH ₂ ) ₆ —. 6 linear lower alkylene groups. R ¹ may have a substituent inert to the reaction, such as an alkoxy group or a keto group, and R ¹ may contain a heteroatom such as oxygen or sulfur in the main chain. A structure separated by a bond, a thioether bond or the like can also be contained.

When R ⁴ and R ⁵ are a hydrogen atom, it represents an aliphatic dicarboxylic acid. Examples of the aliphatic dicarboxylic acid include glutaric acid, adipic acid, pimelic acid, azelaic acid, suberic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, sebacic acid, diglycolic acid, ketopimelic acid, malonic acid, methylmalonic acid, and the like. Can be mentioned. The aliphatic group represented by R ⁴ and R ^5, other linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4, cycloalkyl of 5 to 12 carbon atoms such as cyclohexyl group An alkyl group is mentioned.

Examples of the aromatic group represented by R ⁴ and R ⁵ include a phenyl group and a benzyl group. Among them, R ⁴ and R ⁵ are lower alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of such dialkyl esters include dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, dimethyl pimelate, dimethyl azelate, dimethyl suberate, diethyl suberate, dimethyl sebacate, diethyl sebacate, Examples include dimethyl decanedicarboxylate, dimethyl dodecanedicarboxylate, dimethyl diglycolate, dimethyl ketopimelate, dimethyl malonate, and dimethyl methylmalonate. These may be used alone or in combination of two or more.

(B) Component As (B) component which gives the aliphatic diol residue of Formula (2), an aliphatic diol is mentioned. The aliphatic diol is represented by the following general formula (2 ′).
HO—R ² —OH (2 ′)
(In the formula, R ² represents a divalent aliphatic group having 2 to 12 carbon atoms.)
Examples of the divalent aliphatic group include chain or cyclic alkylene groups having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Preferred alkylene groups are linear lower alkylene groups having 2 to 6 carbon atoms such as — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, and — (CH ₂ ) ₄ —. The divalent aliphatic group R ² can have a substituent inert to the reaction, such as an alkoxy group or a keto group. R ² can contain heteroatoms such as oxygen and sulfur in the main chain, and can also contain, for example, a structure separated by an ether bond, a thioether bond or the like.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 2-methyl-propanediol, 1,4-butanediol, neopentyl glycol, Pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, Pentaethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, and the like can be used. These may be used alone or in combination of two or more.

(C) Component As (C) component which gives the aliphatic hydroxycarboxylic acid residue of Formula (3), it is hydroxycarboxylic acid or hydroxycarboxylic acid ester represented by the following general formula (3 ′), or a cyclic ester thereof. There are certain lactones.
^{R 6 OCO-R 3 -OH (} 3 ')
(In the formula, R ³ represents a divalent aliphatic group having 1 to 10 carbon atoms, and R ⁶ represents a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms or an aromatic group.)
In the formula (3 ′), examples of the divalent aliphatic group R ³ include a chain or cyclic alkylene group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms. R ³ may have a substituent inert to the reaction, such as an alkoxy group or a keto group. R ³ can contain heteroatoms such as oxygen and sulfur in the main chain, and can also contain a structure separated by an ether bond, a thioether bond, or the like.
In the formula (3 ′), R ⁶ is hydrogen, an aliphatic group or an aromatic group. Examples of the aliphatic group include a linear or branched lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms such as a cyclohexyl group, and an aromatic group. , Phenyl group, benzyl group and the like.

Examples of the hydroxycarboxylic acid include glycolic acid, L-lactic acid, D-lactic acid, D, L-lactic acid, 2-methyl lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, 2- Examples include hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxy-3-methylbutyric acid, hydroxypivalic acid, hydroxyisocaproic acid, and hydroxycaproic acid.
The hydroxycarboxylic acid may be a cyclic dimer ester in which two molecules are dehydrated and condensed. Specific examples thereof include lactide obtained from lactic acid and glycolide obtained from glycolic acid.
Examples of the hydroxycarboxylic acid ester include methyl ester and ethyl ester of the above hydroxycarboxylic acid, and acetic acid ester.

Examples of lactones include divalent aliphatic groups having 4 to 10 carbon atoms, preferably 4 to 8 linear or branched alkylene groups. The divalent aliphatic group can have a substituent inert to the reaction, such as an alkoxy group or a keto group, and can contain a heteroatom such as oxygen or sulfur in the main chain. In addition, it may contain a structure separated by a thioether bond or the like.
Specific examples of lactones include, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, 4-methylcaprolactone, 3, 5 , 5-trimethylcaprolactone, various methylated caprolactones such as 3,3,5-trimethylcaprolactone; cyclic monomeric esters of hydroxycarboxylic acids such as β-methyl-δ-valerolactone, enanthlactone and laurolactone; glycolide, L -Cyclic dimer ester of the above hydroxycarboxylic acid such as lactide, D-lactide, etc .; 1,3-dioxolan-4-one, 1,4-dioxane-3-one, 1,5-dioxepan-2-one And the like, and the like. These may be used by mixing two or more monomers.

(Malic acid contained in succinic acid)
In the aliphatic polyester (a) of the present invention, the branch point concentration of a specific structure is controlled to be a specific value or less. The specific branched structure is represented by the following general formula (4)
—O—C (═O) —CH (O—C (═O) —) CH ₂ —C (═O) O— (4)
This is a trifurcated branched structure derived from malic acid. In the linear high molecular weight aliphatic polyester composed of the structural units represented by the formulas (1) to (3), when the branched structure represented by the formula (4) is mixed and the mixing ratio becomes high, it is called ductility. The mechanical characteristics of the molded product are deteriorated, and important physical properties such as impact resistance and tensile elongation at break, which are characteristic of linear polyesters, that is, low-branched aliphatic polyesters, are reduced.

  Since such a branched structure is produced by the presence of malic acid in the raw material to be charged, it can be reduced by reducing or eliminating the abundance. However, succinic acid produced industrially by hydrating maleic anhydride to maleic acid and then hydrogenating maleic acid contains a non-negligible amount of malic acid as an impurity. Succinic acid obtained by such a production method is usually purified by a crystallization method using water or the like as a main solvent, but malic acid as an impurity is not completely removed. Therefore, all the aliphatic polyesters obtained by using succinic acid, which is conventionally available as an industrial raw material, as a main raw material contain a branched structure caused by malic acid.

  Such a branched structure is produced by the presence of malic acid in the charged raw material, but the amount taken into the produced polymer as a branching point varies depending on the raw material species / catalyst used, reaction conditions / process, and the like.

In addition, even when succinic acid is produced biochemically efficiently by fermentation methods as disclosed in JP-A-11-196888 and JP-A-2005-27533, by-product malic acid should be avoided. It is a problem that cannot be done.
That is, to industrially supply a low-branched high molecular weight aliphatic polyester excellent in mechanical properties of a molded product, it is important to reduce the malic acid concentration in succinic acid available as an industrial raw material.
In the present invention, molding of the resin and the composition thereof according to the present invention by setting the mixing ratio of malic acid to succinic acid as a main raw material or its derivative (A ′) that can participate in polymerization to a specific value or less. In addition to improving the ductility and impact resistance of the product, the variation can be dramatically improved.

In the present invention, the mixing ratio of malic acid in the total of 100 mol% of the raw material (A) and the raw material (C) is 0.60 mol% or less, preferably 0.35 mol% or less, more preferably 0.21 mol% or less. To do.
Thereby, by optimizing the reaction conditions and processes to be adopted, the content of the branched structure represented by the formula (4) in the obtained low-branched high molecular weight aliphatic polyester (a) is reduced to the numerical range or less. can do.
At this time, in particular, when the succinic acid or its derivative (A ′) that can participate in polymerization is succinic acid or succinic anhydride, usually 0.005 mol% or more of malic acid is mixed. In order to obtain industrially inexpensively, it can be preferably used even if the mixing ratio of malic acid is 0.05 mol% or more as long as it is within the above range.
For example, when succinic acid is produced and used industrially, it is necessary to recrystallize the solvent and purify it to reduce the mixing ratio of malic acid within the above range. The recrystallization solvent is not particularly limited as long as it can dissolve succinic acid and malic acid, and water, alcohol, ether, ketone, ester, ether ester and other organic solvents, and mixtures thereof can be used. Water or a mixture of water and the above organic solvent can be preferably used.

  The aliphatic polyester (a) or the low molecular weight aliphatic polyester (a ′) obtained by the polymerization reaction of the component (A), component (B), and component (C) added as necessary in the present invention In the case of a polymer, the copolymerization mode may be random or block, but is preferably a random copolymer. The above monomers may be charged all at once (randomly), dividedly charged (blocked), or a lactone may be polymerized to a dicarboxylic acid-diol polymer, or the polylactone may be polymerized by adding a dicarboxylic acid and a diol. .

  When the low molecular weight aliphatic polyester (a ′) is synthesized by the polymerization reaction of the three components (A), (B), and (C) in the present invention, the synthesis step depends on the type of raw materials used, for example, The esterification step in which the first half of the dehydration reaction mainly proceeds and the polycondensation step in which the latter half of the transesterification reaction mainly proceeds can be divided.

The esterification step is performed at a reaction temperature of 80 ° C. to 250 ° C., preferably 100 ° C. to 240 ° C., more preferably 145 ° C. to 230 ° C., for 0.5 to 5 hours, preferably 1 to 4 hours, 760 to 100 Torr. It is desirable to do below. Although a catalyst is not necessarily required, it is used in an amount of 10 ⁻⁷ to 10 ⁻³ mol, preferably 10 ^{−6 to} 5 × 10 ⁻⁴ mol, relative to 1 mol of an aliphatic dicarboxylic acid or diester used as a raw material. May be.

The latter polycondensation step is desirably completed in 2 to 10 hours, preferably 3 to 6 hours by raising the reaction temperature while reducing the pressure of the reaction system, and finally 180 ° C to 270 ° C, preferably 190 ° C. The degree of vacuum is 3 Torr or less, preferably 1 Torr or less at a reaction temperature of ˜240 ° C. In this step, it is preferable to use a general transesterification reaction catalyst, and it is 10 ⁻⁷ to 10 ⁻³ mol, preferably 10 ^{−6 to} 5 ×, per 1 mol of the aliphatic dicarboxylic acid or diester used as a raw material. ^{Used in} an amount of ^10-4 mol. When the amount of the catalyst is less than this range, the reaction does not proceed well, and the reaction takes a long time. On the other hand, if it exceeds this range, it causes thermal decomposition, crosslinking, coloring, etc. of the polymer during polymerization, and also causes thermal decomposition in the molding process of the polymer.

  Examples of catalysts that can be used in both the esterification step in which the dehydration reaction mainly proceeds in the synthesis step and the polycondensation step in which the latter transesterification reaction mainly proceeds include the following specific examples. However, these catalysts may be used alone or in combination of two or more. As the catalyst, those described in WO 02-44249 can be used. Among them, by using a mixed catalyst composed of a titanium compound and a phosphorus compound and / or a magnesium compound as a catalyst, the polymerization rate is increased, so that a product having few heterogeneous bonds such as an ether bond formed by a side reaction can be obtained. Is particularly preferable. In this case, the Mg / Ti atomic ratio is preferably in the range of 0.05 to 2.0 mol times, preferably 0.1 to 1.2 mol times, more preferably 0.2 to 0.8 mol times. It is a range. If the Mg / Ti atomic ratio is less than 0.05 mol times, the resulting resin may be colored. Conversely, if it exceeds 2.0 mol times, the reaction rate becomes slow.

In the step of synthesizing the aliphatic polyester (a) or (a ′), the charging ratio of the raw material (A) component and the (B) component is preferably selected so as to meet the following conditional expression (i).
1.0 ≦ [B] / [A] ≦ 2.0 (i)
(In the formula, [A] represents the number of moles of component (A), and [B] represents the number of moles of component (B).)
When the value of [B] / [A] is smaller than 1, a large amount of low molecular weight oligomers having both ends at carboxylic acid ends are formed, and no further esterification reaction or polycondensation reaction proceeds, and fat having a desired molecular weight Group polyester (a) or (a ′) is difficult to obtain, and when the value of [B] / [A] is greater than 2, the glycol end concentration at the end of the first half esterification step is excessively large. A long reaction time is required for the polycondensation step.

In the present invention, in order to finally obtain an aliphatic polyester (a) having practical strength, the difunctional bifunctional compound represented by the above formula (7) is added to the low molecular weight aliphatic polyester (a ′) in a molten state. A linking agent (e) may be added to increase the weight average molecular weight to the high molecular weight.
The low molecular weight aliphatic polyester (a ′) used for the ligation reaction has a weight average molecular weight of 5,000 or more, preferably 10,000 or more. When the molecular weight is smaller than 5,000, the end group concentration of the low molecular weight aliphatic polyester (a ′) is high, and a large amount of a linking agent is required. When the amount of the binder used is large, problems such as gelation are likely to occur. When the sum of the acid value and the hydroxyl value is 1.0 or less, the viscosity of the molten state becomes high because the molecular weight of the low molecular weight aliphatic polyester (a ′) is high. In this case, the amount of the binder used is extremely small, so that it is difficult to cause a uniform reaction, and problems such as gelation are likely to occur.

The linking agent (e) used in the present invention is represented by the formula (7). However, those that function more than 3 functions are excluded. As the reactive groups X ¹ and X ² of the linking agent (e), formulas (9) to (11) that can react with a hydroxyl group to form a covalent bond:

General groups (12) to (15) capable of forming a covalent bond by reacting with a reactive group and / or a carboxyl group

(R ^{8 to} R ¹⁰ represent a divalent aliphatic group or an aromatic group, and hydrogen directly bonded to the ring may be substituted with an aliphatic and / or aromatic group) 3 It can be selected from a group of ˜8-membered cyclic reactive groups. X ¹ and X ² may have the same chemical structure or may be different.

As the linking agent (e), various linking agents described in WO 02-44249, such as a series of diisocyanate compounds, can be used.
The diisocyanate compound is preferably an aliphatic diisocyanate compound. Specifically, hexamethylene diisocyanate, lysine diisocyanate methyl ester {OCN— (CH ₂ ) ₄ —CH (—NCO) (— COOCH ₃ )}, trimethylhexa Examples include methylene diisocyanate, and hexamethylene diisocyanate is particularly preferable.

The reaction between the linking agent (e) and the low molecular weight aliphatic polyester (a ′) is carried out under conditions where the low molecular weight aliphatic polyester (a ′) can be easily stirred in a uniform molten state or containing a small amount of solvent. It is desirable to be performed at. The amount of the binder (e) used is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the low molecular weight aliphatic polyester (a ′). If the amount of the linking agent (e) is smaller than this, it is difficult to obtain a final product having a desired molecular weight, and if it is large, problems such as gelation are likely to occur.
The reaction for increasing the molecular weight using the linking agent (e) is carried out at a melting point or higher of the low molecular weight aliphatic polyester (a ′) and carried out at 270 ° C. or lower, preferably 250 ° C. or lower, more preferably 230 ° C. or lower. Can do. This reaction can be carried out in the same reactor as the polycondensation reaction by adding the linking agent (e) to the reactor in which the low molecular weight aliphatic polyester has been produced. Moreover, it can also be carried out by mixing the low molecular weight aliphatic polyester and the binder using an ordinary extruder or static mixer.

The low-branching high-molecular weight aliphatic polyester (a) of the present invention is prepared by using a biaxial continuous polymerization reactor in the high-molecular weight process in which the viscosity of the reaction solution is 10 Pa · sec or more, thereby connecting the binder (e ) Can be more efficiently produced.
The reaction temperature of the polycondensation reaction is 220 to 250 ° C. When the reaction temperature exceeds 250 ° C., the reaction proceeds fast, but side reactions become intense, resulting in not only an increase in the acid value of the polymer obtained and a decrease in molecular weight, but also the formation of heterogeneous bonds such as ether bonds. It cannot be ignored and the quality deteriorates. When the reaction temperature is lower than 220 ° C., the progress of the deglycolization reaction is slow and the molecular weight does not increase to a predetermined value. Moreover, the viscosity of the reaction system becomes high and stirring becomes difficult, which is not preferable. In addition, it is not preferable because a heterogeneous bond such as an ether bond increases due to a long reaction time.
Further, the degree of reduced pressure in the high molecular weight process using the biaxial continuous reaction apparatus is 5 mmHg, preferably 3 mmHg or less, more preferably 1.5 mmHg or less. The higher the degree of vacuum, the more preferable is the ability to suppress the formation of heterogeneous bonds such as ether bonds.

  Examples of the biaxial continuous polymerization reaction apparatus that can be used include a self-cleaning reactor (“SCR” manufactured by Mitsubishi Heavy Industries, Ltd.) in which the stirring blade is an eccentric disk, and the stirring blade is a hollow disk blade or a three-blade blade. (“HVR” manufactured by Mitsubishi Heavy Industries, Ltd.), horizontal twin-shaft reactor (manufactured by Mitsubishi Heavy Industries, Ltd.), KRC kneader (manufactured by Kurimoto Steel Corporation), TEX-K (manufactured by Nippon Steel Works, Ltd.), hybrid type Examples include a reactor (manufactured by Hitachi, Ltd.), a Hitachi glasses blade polymerizer (manufactured by Hitachi, Ltd.), a Hitachi lattice blade polymerizer (manufactured by Hitachi, Ltd.), and the like. These apparatuses are advantageous in that the deglycolization reaction proceeds smoothly and increases to the desired molecular weight because the surface of the polymer is efficiently renewed inside.

In the present invention, when the component (C) is used, it is preferable to select the charging ratio of the raw material (A) component and the (C) component so as to meet the following conditional expression (ii).
0 ≦ [C] / ([A] + [C]) ≦ 0.25 (ii)
(In the formula, [A] represents the number of moles of component (A) used, and [C] represents the number of moles of component (C) used.)
[C] / ([A] + [C]) in the above formula is when the aliphatic polyester (a) or (a ′) is composed of the repeating unit (P) and the repeating unit (Q). Represents the molar fraction of the repeating unit Q.
In particular, when the repeating unit (Q) (that is, the structural unit represented by (3)) is included, it is preferably 0.04 to 0.25, more preferably 0.06 to 0.23, and particularly preferably 0.08. ~ 0.20.
When this value is larger than 0.25, the melting point of the resulting polymer is low, and the crystallinity is extremely lowered, so that it has no heat resistance and is unsuitable for practical use. When this value is larger than 0.04, a more practical polymer having appropriate flexibility and biodegradability can be obtained.

The aliphatic polyester (a) according to the present invention preferably has a weight average molecular weight of 200,000 or more. The melting point is usually 80 ° C. or higher, and thermoforming is easy.
In the aliphatic polyester used in the present invention, in particular, R ¹ and R ² in the general formulas (1) to (3) are (CH ₂ ) ₂ or (CH ₂ ) ₄ , and R ³ is (CH _{2). 5} ) Those having ₅ have a high melting point and high crystallinity. Specifically, polybutylene succinate, poly (butylene succinate-butylene adipate) copolymer, poly (butylene succinate-ε-caprolactone) copolymer, poly (butylene succinate-lactic acid) copolymer, poly Examples include (butylene succinate-butylene adipate-lactic acid) copolymer and / or polyethylene succinate. The aliphatic polyester (a) is preferably polybutylene succinate depending on application conditions such as heat resistance, flexibility and biodegradability.

In this invention, it can be set as the low-branching high molecular weight aliphatic polyester composition which mix | blended the following various additives with aliphatic polyester (a) as needed.
Additives include plasticizers, heat stabilizers, lubricants, anti-blocking agents, nucleating agents, photodegradants, biodegradation accelerators, antioxidants, UV stabilizers, antistatic agents, flame retardants, drop agents, antibacterial agents , Deodorants, fillers, colorants, or mixtures thereof.
Examples of the plasticizer include aliphatic dibasic acid esters, phthalic acid esters, hydroxy polycarboxylic acid esters, polyester plasticizers, fatty acid esters, epoxy plasticizers, and mixtures thereof. Specifically, phthalic acid esters such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP), adipic acid-di-2-ethylhexyl (DOA), diisodecyl adipate (DIDA) and other adipic acid esters, azelaic acid-di-2-ethylhexyl (DOZ) and other azelaic acid esters, acetyltricitrate tri-2-ethylhexyl, acetylcitrate tributyl and other hydroxypolycarboxylic acid esters, polypropylene glycol Polyester plasticizers such as adipic acid esters, which are used alone or in a mixture of two or more.
The amount of these plasticizers added is preferably in the range of 5 to 15 parts by weight for a film. If it is less than 3 parts by weight, the elongation at break and impact strength are lowered, and if it exceeds 30 parts by weight, the break strength and impact strength may be reduced.

Thermal stabilizers include aliphatic carboxylates. As the aliphatic carboxylic acid, an aliphatic hydroxycarboxylic acid is particularly preferable. As the aliphatic hydroxycarboxylic acid, naturally occurring ones such as lactic acid and hydroxybutyric acid are preferable.
Examples of the salt include salts of sodium, calcium, aluminum, barium, magnesium, manganese, iron, zinc, lead, silver, copper and the like. These can be used as one kind or a mixture of two or more kinds.
As addition amount, it is the range of 0.5-10 weight part with respect to 100 weight part of aliphatic polyester (a). When the heat stabilizer is used within the above range, the impact strength (Izod impact value) is improved, and there is an effect that variations in breaking elongation, breaking strength, and impact strength are reduced.

As the lubricant, those generally used as an internal lubricant and an external lubricant can be used. For example, fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, fatty alcohol, many Examples thereof include monohydric alcohols, polyglycols, polychrycerols, metal soaps, modified silicones, or mixtures thereof. Preferably, fatty acid ester, hydrocarbon resin, etc. are mentioned.
The blending amount is 0.05 to 5 parts by weight of a lubricant with respect to 100 parts by weight of the resin as a film. If it is less than 0.05 parts by weight, the effect is not sufficient, and if it exceeds 5 parts by weight, it will not be wound on the roll, and the physical properties will also deteriorate.
For films, ethylenebisstearic acid amide, stearic acid amide, oleic acid amide, and erucic acid amide that are highly safe and registered with the FDA (US Food and Drug Administration) are preferable from the viewpoint of preventing environmental pollution.

Examples of the photodegradation accelerator include benzophenones such as benzoins, benzoin alkyl ethers, benzophenone, 4,4-bis (dimethylamino) benzophenone and derivatives thereof; acetophenones such as acetophenone and α, α-diethoxyacetophenone; Examples thereof include photoexciters such as quinones; thioxanthones; phthalocyanines, anatase-type titanium oxide, ethylene-carbon oxide copolymers, and sensitizers of aromatic ketones and metal salts. These photodegradation accelerators can be used alone or in combination of two or more.
Examples of the biodegradation accelerator include oxo acids (eg, oxo acids having about 2 to 6 carbon atoms such as glycolic acid, lactic acid, citric acid, tartaric acid, malic acid), saturated dicarboxylic acids (eg, oxalic acid, malon, etc.). Organic acids such as acids, succinic acid, succinic anhydride, glutaric acid and the like, such as lower saturated dicarboxylic acids having about 2 to 6 carbon atoms, etc .; lower alkyl esters of these organic acids and alcohols having about 1 to 4 carbon atoms included. Preferred biodegradation accelerators include organic acids having about 2 to 6 carbon atoms such as citric acid, tartaric acid, malic acid, and coconut shell activated carbon. These biodegradation accelerators can be used alone or in combination of two or more.

Examples of the filler (including a bulking agent and an antiblocking agent) include various fillers such as calcium carbonate and talc, mica, calcium silicate, fine powder silica (anhydride), white carbon (hydrated substance), Examples thereof include inorganic fillers such as asbestos, porcelain clay (baked), barley stone, various titanium oxides, and glass fibers, and organic fillers such as particles of natural materials. In order to prevent blocking, the particle diameter is preferably 0.1 to 7 μm. The fine powder silica as the inorganic filler may be a silica produced by a wet method or a silica produced by high-temperature hydrolysis of silicon tetrachloride in an oxyhydrogen flame.
Addition of inorganic fillers further improves biodegradability and increases melt strength (viscosity), preventing drawdown during melt molding and providing moldability such as vacuum molding, blow molding, and inflation molding. improves.

  Further, by adding an inorganic filler such as talc, a film excellent in slipping property can be obtained without significantly impairing impact resistance. Specifically, the friction coefficient in accordance with JIS K7125 is preferably 0.1 to 0.5, more preferably 0.15 to 0.4, and most preferably on both the front and back surfaces of the film. Can obtain a film of 0.2-0.3.

  When the coefficient of friction is too large, unwinding of the film from the roll shape cannot be performed smoothly, resulting in deterioration of usability and sometimes causing breakage of the film. When the coefficient of friction is too small, handling problems such as roll slippage occur when the film is wound into a roll.

  The addition amount of the filler is not particularly limited, but the weight ratio represented by the filler / aliphatic polyester (a) is 0.01 to 60 / 99.99 to 40 (for example, 0.1 to 60). /99.9-40, 1-60 / 99-40) preferably 3-50 / 97-50, more preferably 5-45 / 95-55.

Organic fillers include fine powder particles made from paper having a diameter of 50 microns or less. The addition amount and particle size of the organic filler are the same as those of the inorganic filler.
Examples of the bulking agent include wood powder and glass balloon. The addition amount of the extender is the same as that of the inorganic filler.

  The aliphatic polyester (a) and the additive may be kneaded or molded without kneading. As a kneading method, a general method can be preferably used. Specifically, raw resin pellets, powders, solid strips, and the like are dry-mixed with a Henschel mixer or a ribbon mixer, and a single or twin screw extruder or Banbury. It can supply to known melt mixers, such as a mixer, a kneader, a mixing roll, and can melt-knead.

<Low branching high molecular weight aliphatic polyester molded product>
The molded article of the present invention is obtained by extrusion molding, injection molding, compression molding, injection compression molding, transfer molding, cast molding, a resin composition with the aliphatic polyester (a) or an additive added as necessary. It can be obtained by stampable molding, blow molding, stretched film molding, inflation film molding, laminate molding, calendar molding, foam molding, RIM molding, FRP molding, powder molding or paste molding.

  The film of the present invention is obtained by film-forming the above composition by T-die molding, inflation molding, calendar molding, extrusion lamination molding or the like. The film of the present invention has a thickness of 5 μm to 1 mm, preferably 10 to 100 μm.

The film of the present invention includes a sheet, a film and a tape. Moreover, although a film is used also by a single layer, a laminated body with another base material may be sufficient. When obtaining a laminated film, a film having heat-fusibility obtained from the resin composition according to the present invention and another substrate may be used as a coextruded film using a multilayer die. Further, the resin composition may be extruded and laminated on a substrate obtained in advance to form a laminated film, or a film obtained separately may be bonded to form a laminated film. In addition, as a base material, a film, a sheet, a cup, a tray-like product obtained from an aliphatic polyester such as polylactic acid or an aromatic polyester such as polyethylene terephthalate, or a foam thereof, glass, metal, aluminum foil, paper, etc. Can be mentioned. When the base material is a film made of a thermoplastic resin, it may be unstretched or may be a uniaxial or biaxially stretched film. Of course, the substrate may be a single layer or two or more layers.
The film of the present invention is excellent in transparency, and is an original film for bag making of shopping bags, an original film for bag making of packaging bags, an original film for bag making of garbage bags, or a house film for agriculture formed by secondary molding. It can be processed into agricultural multi-films, label films and the like.

  The molded article of the present invention has the following characteristics. When the elastic deformation energy Ep (unit: J) and the propagation energy Eg after elastic deformation (unit: J) are measured by a falling cone impact test based on ASTM D3763 on a press molded plate having a thickness of 1.5 mm, Ep + Eg is 10 J As mentioned above, Preferably it is 11J or more, More preferably, it is 12J or more. Further, the propagation energy Eg is 5.5 J or more, preferably 6.0 J or more, and more preferably 7.0 J or more.

Annealing treatment The film obtained above may be annealed. Although it depends on the composition ratio, the annealing temperature is usually in the range of 30 to 60 ° C., preferably 35 to 50 ° C., and more preferably 35 to 45 ° C. If it is higher than 60 ° C., the film becomes too soft and may be blocked. The annealing treatment time is usually 10 hours or longer, preferably 24 to 480 hours, more preferably 72 to 360 hours, although it depends on the temperature. The upper limit is not particularly limited, but the effect is saturated when it exceeds 480 hours.

Physical properties of molded product The molded product of the present invention has the following characteristics.
(1) The average value of elongation at break by a high-speed tensile test (Daicel method) in the TD direction of the film is 750% or more, preferably 770% or more, and more preferably 800% or more. Further, the variation is a fluctuation rate of 15% or less, preferably 13% or less, more preferably 10% or less.
(2) The average value of absorbed energy by a Charpy impact test (Daicel method) in the TD direction of the film is 150 MPa (1530 kg / cm ² ) or more, preferably 170 MPa (1734 kg / cm ² ) or more, more preferably 200 MPa (2040 kg / cm ² ). cm ² ) or more. Further, the variation is 50% or less, preferably 45% or less, and more preferably 40% or less in terms of variation.

Physical properties of film The mechanical properties of the film of the present invention are as follows.
(I) In a film having a thickness of 20 μm, each physical property value obtained by a tensile test described below (based on JIS K6781) is as follows:
Tensile modulus: 50 to 500 MPa, preferably 100 to 400 MPa
Stress at break: 10 to 40 MPa, preferably 15 to 30 MPa
Elongation at break: 100-2000%, preferably 300-1500%
Tear strength: 0.2-5N, preferably 0.5-3N
(Ii) Each physical property value obtained by a tensile test (based on JIS K6781) described later in a film having a thickness of 40 μm is as follows:
Tensile modulus: 50 to 500 MPa, preferably 100 to 400 MPa
Stress at break: 10 to 40 MPa, preferably 15 to 30 MPa
Elongation at break: 100-3000%, preferably 500-2000%
Tear strength: 0.2-5N, preferably 0.5-3N.

The inflation film of the present invention has the following characteristics.
(Falling ball impact test)
(I ′) In a film having a thickness of 20 μm, numerical values according to a falling ball impact test (test method will be described later) are as follows:
H (d = thickness) when using a falling ball of φ41 mm and 286 g is 5 cm or more, preferably 10 to 50 cm
H (d = thickness) when using a falling ball of φ19 mm and 28 g is 20 cm or more, preferably 30 to 500 cm
(Ii ′) A film having a thickness of 40 μm, and numerical values according to a falling ball impact test (test method will be described later) are as follows:
H (d = thickness) when using a falling ball of φ41 mm and 286 g is 8 cm or more, preferably 10 to 1000 cm
H (d = thickness) when using a falling ball of φ19 mm and 28 g is 30 cm or more, preferably 50 to 2000 cm.

(Heat shrinkage test)
(Iii ′) In a film having a thickness of 20 μm, the thermal shrinkage stress (SMD) in the MD direction is 0.35 MPa or less, preferably 0.3 MPa or less, more preferably 0.25 MPa or less. The ratio SMD / STD to STD) is 10 or less, preferably 7.5 or less, more preferably 5 or less.

  Since there is no formula for accurately estimating each physical property value of a film having an arbitrary thickness from the physical property value of a film having a thickness of 20 μm or 40 μm, a film of an arbitrary aliphatic polyester resin is an aliphatic group according to the present invention. As a criterion for judging whether or not the polyester film falls within the range, a physical property value when a film having a thickness of 20 μm is formed is used as a criterion. In the present invention, “when converted to a thickness of 20 μm” has this meaning.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
First, although the low branching high molecular weight aliphatic polyester composition of the present invention will be specifically described with reference to production examples, the composition of the present invention is not limited thereto. Each characteristic value in the production example or the production comparative example is measured by the following method.

(1) Malic acid in succinic acid Malic acid in succinic acid was quantified by an ion chromatography apparatus equipped with an electrical conductivity detector as a detector. As the eluent, 1 mM / L octanesulfonic acid was used, and as the column, IonPac ICE-AS1 manufactured by Nippon Dainex Co., Ltd. was used.

(2) Molecular weight and molecular weight distribution Number average molecular weight (Mn) using a calibration curve prepared from standard polystyrene by a gel permeation chromatography (GPC) apparatus equipped with a differential refractive index system and a differential pressure viscometer as a detector. The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined. Chloroform was used as an eluent, and three Shodex 806L manufactured by Showa Denko Co., Ltd. were connected and used as a column.
When calculating the molecular weight (Mn, Mw) and molecular weight distribution (Mw / Mn) from the elution curve, the peak start point and end point are determined from the elution curve by the differential pressure viscometer, and each of the points from the start point to the end point is determined. Molecular weight (Mn, Mw) and molecular weight distribution (Mw / Mn) were calculated from the response intensity of the differential refractometer at the elution time. In FIG. 5, the upper part is an elution curve obtained with a differential refractometer, and the lower part is an elution curve obtained with a differential pressure viscometer.

(3) Acid value It measured based on JISK0070.

(4) Polymer composition, hydroxyl group terminal concentration, branch point concentration, ether bond concentration
^{From the 1} H-NMR spectrum, the molar fraction of each monomer unit contained in the polymer was calculated from the area of the peak derived from each monomer used, and the polymer composition was determined therefrom. Moreover, the hydroxyl group terminal concentration, the branching point concentration, and the ether bond concentration were calculated from the peaks derived from the hydroxyl terminal, the branched structure, and the ether bond.
FIG. 4 is an example of a ¹ H-NMR spectrum of the aliphatic polyester (a) of the present invention using 1,4-butanediol, succinic acid, and ε-caprolactone as main raw materials. In FIG. 4, the peak c derived from the hydroxyl end is shown enlarged at a magnification of 100 times in the vertical direction and 2 times in the horizontal direction. Similarly, a branched structure represented by the following formula (4) derived from malic acid mixed as an impurity in succinic acid:
—O—C (═O) —CH (O—C (═O) —) CH ₂ —C (═O) O— (4)
The peak “e” based on is enlarged at a magnification of 500 times in the vertical direction and 2 times in the horizontal direction. Similarly, the peak f derived from the by-product ether bond is shown enlarged at a magnification of 200 times in the vertical direction and 2 times in the horizontal direction.
As can be seen from the figure, the peak of the two methylene groups adjacent to the oxygen atom of the 1,4-butanediol residue overlaps the peak of the ε-methylene group adjacent to the oxygen atom of the ε-caprolactone residue. Is observed as a peak d (triplet) at 4.07 ppm. On the other hand, the peak of the α-methylene group adjacent to the carbonyl group of the ε-caprolactone residue is observed as a peak a (triplet) at 2.28 ppm. Further, two equivalent methylene group peaks of the succinic acid residue are observed as a peak b (triplet) at 2.57 ppm.
The peak of the α-methylene group adjacent to the hydroxyl group is observed as a peak c (triplet) at 3.61 ppm. With regard to the branched structure of the formula (4), a methine group peak is observed as a peak e (triplet) at 5.43 ppm. In addition, two equivalent methylene group peaks adjacent to the ether oxygen of the by-product ether bond are observed as a peak f (triplet) at 3.37 ppm.

(5) Melting point The melting point was determined by a differential scanning calorimeter (DSC). Specifically, 3 to 6 mg was collected from the high molecular weight aliphatic polyester pellet of the present invention and subjected to measurement. The pellet is first cooled from room temperature to −120 ° C. at a rate of 20 ° C./min (cooling process 1), then held at −120 ° C. for 3 minutes and then from −120 ° C. at a rate of 20 ° C./min. The temperature was raised to 220 ° C. (temperature raising process 1). Subsequently, the sample was held at 220 ° C. for 3 minutes, then cooled again to −120 ° C. at a rate of 20 ° C./min (cooling process 1), held at −120 ° C. for 3 minutes, and then again at a rate of 20 ° C./min. The temperature was raised from −120 ° C. to 220 ° C. (temperature raising process 2), and the measurement was completed. The melting point was determined as the peak top of the endothermic peak appearing in the temperature raising process 2.

[Production Example 1]
After replacing the inside of the jacketed vertical reactor equipped with paddle blades with nitrogen, 43.18 kg of succinic acid containing 0.35% by weight of malic acid (the malic acid concentration with respect to the total acid components at the time of charging is 0.31 mol%), First, 36.25 Kg of 1,4-butanediol, 36.35 g of titanium tetraisopropoxide, and 7.43 g of magnesium hydrogen phosphate trihydrate (MgHPO ₄ .3H ₂ O) were charged, and gradually from room temperature in a nitrogen atmosphere. The temperature was raised to 240 ° C.
After starting the temperature increase, the reaction liquid temperature reached 141 ° C. in 1.5 hours, and the distillation of water started. The esterification reaction was completed when the amount of distilled water reached 13.0 kg in 5.5 hours after the start of temperature increase.
The aliphatic polyester low molecular weight product obtained by the esterification reaction is transferred to a high-viscosity batch polymerization machine, the temperature of the reaction solution is kept at 240 ° C., and gradually reduced from normal pressure to 1.0 mmHg (133 Pa). And the polycondensation reaction was carried out by stirring for 4.5 hours. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
The pelletized polymer was further fed to an extruder at a flow rate of 7.4 Kg / h by a quantitative feeder and melted, and then fed into a biaxial continuous polymerization reactor (glassware blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L). Continuously fed. Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The treatment liquid was continuously discharged from the reaction apparatus, and a pelletized high molecular weight polymer was obtained through cooling in a water tank and cutting with a cutter.
After the pelletized polymer having a high molecular weight by the spectacle blade polymerizer was melted by feeding it to the extruder at a flow rate of 7.4 kg / h by a quantitative feeder, another biaxial continuous polymerization reactor (Hitachi Co., Ltd.) Continuously supplied to a lattice blade polymerization machine manufactured by Seisakusho, standard tension amount 6 L). Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The polymer having a higher molecular weight in the reaction apparatus was continuously discharged from the reaction apparatus, cooled in a water tank, and cut with a cutter to obtain the desired high molecular weight aliphatic polyester pellets.
The aliphatic polyester (polybutylene succinate) had a weight average molecular weight of 221,000, a molecular weight distribution of 2.37, and an acid value of 1.1 mgKOH / g. When the structural unit derived from the raw material monomer was expressed as 100 mol%, it was 49.7 mol% succinic acid residue and 50.3 mol% 1,4-butanediol residue. The hydroxyl terminal concentration was 13.8 × 10 ⁻⁶ mol / g, the branch point concentration was 3.9 × 10 ⁻⁶ mol / g, and the ether bond concentration was 0.8 × 10 ⁻⁶ mol / g. The melting point was 114.2 ° C.

[Production Example 2]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 40.00 kg of succinic acid containing 0.35% by weight of malic acid, 32.05 kg of 1,4-butanediol, 9.67 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide and 4.92 g of magnesium hydrogenphosphate trihydrate were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.25 mol%. The esterification reaction is carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product is transferred to a high viscosity batch polymerization machine, the temperature of the reaction solution is kept at 240 ° C., and the pressure is gradually reduced from normal pressure. Finally, the mixture was stirred at 1.0 mmHg (133 Pa) for 5.0 hours to perform a polycondensation reaction. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
After the obtained pellet-like polymer was melted by feeding to an extruder at a flow rate of 7.4 kg / h by a quantitative feeder, a biaxial continuous polymerization reactor (glasses blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L) ) Continuously. Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The polymer having a high molecular weight was continuously discharged from the reaction apparatus, and was cooled in a water tank and cut with a cutter to obtain a pellet-shaped high molecular weight aliphatic polyester.
The aliphatic polyester had a weight average molecular weight of 205,000, a molecular weight distribution of 2.33, and an acid value of 1.0 mgKOH / g. The polymer copolymer composition was 80.7 mol% of butylene succinate unit, 19.3 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 44.6 mol%, 1,4-butane Diol residue 44.7 mol%, ε-caprolactone residue 10.7 mol%), the hydroxyl group terminal concentration is 19.1 × 10 ⁻⁶ mol / g, and the branching point concentration is 4.7 × 10 ⁻⁶ mol / g. The ether bond concentration was 0.8 × 10 ⁻⁶ mol / g. The melting point was 91.6 ° C.

[Production Example 3]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 34.54 kg of succinic acid containing 0.35% by weight of malic acid, 10.69 kg of adipic acid, 36.25 kg of 1,4-butanediol, titanium 36.35 g of tetraisopropoxide and 9.14 g of magnesium acetate tetrahydrate (Mg (OAc) ₂ .4H ₂ O) were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.25 mol%. The esterification reaction is carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product is transferred to a high viscosity batch polymerization machine, the temperature of the reaction solution is kept at 240 ° C., and the pressure is gradually reduced from normal pressure. Finally, the mixture was stirred at 1.0 mmHg (133 Pa) for 5.0 hours to perform a polycondensation reaction. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
After the obtained pellet-like polymer was melted by feeding to an extruder at a flow rate of 7.4 kg / h by a quantitative feeder, a biaxial continuous polymerization reactor (glasses blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L) ) Continuously. Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The polymer having a high molecular weight was continuously discharged from the reaction apparatus, and was cooled in a water tank and cut with a cutter to obtain a pellet-shaped high molecular weight aliphatic polyester.
The aliphatic polyester had a weight average molecular weight of 207,000, a molecular weight distribution of 2.30, and an acid value of 0.6 mgKOH / g. The polymer copolymer composition was 79.8 mol% of butylene succinate units, 20.2 mol% of butylene adipate units (39.9 mol% of succinic acid residues and 10.1 mol of adipic acid residues when expressed as 100 mol% of structural units derived from raw material monomers). 1 mol%, 1,4-butanediol residue 50.0 mol%), the hydroxyl group terminal concentration is 19.6 × 10 ⁻⁶ mol / g, the branch point concentration is 2.3 × 10 ⁻⁶ mol / g, ether The binding concentration was 1.0 × 10 ⁻⁶ mol / g. The melting point was 90.4 ° C.

[Production Example 4]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 38.00 kg of succinic acid containing 0.35 wt% of malic acid, 30.45 kg of 1,4-butanediol, L-lactic acid (90% aqueous solution) ) 3.89 Kg, titanium tetraisopropoxide 48.14 g and magnesium hydrogen phosphate trihydrate 9.35 g were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the whole acid component at the time of preparation was 0.28 mol%. The esterification reaction was carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product was transferred to a high viscosity batch polymerization machine, the temperature of the reaction solution was kept at 240 ° C., and the pressure was gradually reduced from normal pressure. Finally, the polycondensation reaction was carried out by stirring at 1.0 mmHg (133 Pa) for 4.5 hours. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
The pelletized polymer was further fed to an extruder at a flow rate of 7.4 Kg / h by a quantitative feeder and melted, and then fed into a biaxial continuous polymerization reactor (glassware blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L). Continuously fed. Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The treatment liquid was continuously discharged from the reaction apparatus, and a pelletized high molecular weight polymer was obtained through cooling in a water tank and cutting with a cutter.
After the pelletized polymer having a high molecular weight by the spectacle blade polymerizer was melted by feeding it to the extruder at a flow rate of 7.4 kg / h by a quantitative feeder, another biaxial continuous polymerization reactor (Hitachi Co., Ltd.) Continuously supplied to a lattice blade polymerization machine manufactured by Seisakusho, standard tension amount 6 L). Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The polymer further polymerized in the reaction apparatus was continuously discharged from the reaction apparatus, and after cooling in a water tank and cutting with a cutter, the desired high molecular weight aliphatic polyester pellets were obtained.
The aliphatic polyester had a weight average molecular weight of 224,000, a molecular weight distribution of 2.38, and an acid value of 1.1 mgKOH / g. The polymer copolymer composition was 91.7 mol% of butylene succinate units, 8.3 mol% of lactic acid units (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 47.8 mol%, 1,4-butanediol residue Group 47.9 mol%, lactic acid residue 4.3 mol%), hydroxyl group terminal concentration 15.6 × 10 ⁻⁶ mol / g, branch point concentration 5.9 × 10 ⁻⁶ mol / g, ether bond concentration Was 1.3 × 10 ⁻⁶ mol / g. The melting point was 104.7 ° C.

[Production Example 5]
After replacing the inside of a jacketed vertical reaction vessel equipped with paddle blades with nitrogen, 38.00 kg of succinic acid containing 0.35 wt% of malic acid, 31.91 kg of 1,4-butanediol, 5.98 kg of ε-caprolactone, L-lactide 1.33 kg and titanium tetraisopropoxide 48.14 g were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.25 mol%. The esterification reaction was carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product was transferred to a high viscosity batch polymerization machine. The temperature of the reaction solution was maintained at 225 to 245 ° C., and the pressure was gradually reduced from normal pressure. Finally, the polycondensation reaction was performed by stirring at 1.0 mmHg (133 Pa) for 6.0 hours. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-like high molecular weight aliphatic polyester.
The aliphatic polyester had a weight average molecular weight of 237,000, a molecular weight distribution of 2.42, and an acid value of 1.4 mgKOH / g. The polymer copolymer composition was 84.8 mol% of butylene succinate units, 11.3 mol% of ε-caprolactone units, 3.9 mol% of lactic acid units. %, 1,4-butanediol residue 46.2 mol%, ε-caprolactone residue 6.1 mol%, lactic acid residue 2.1 mol%), and the hydroxyl group terminal concentration is 7.5 × 10 ⁻⁶ mol / g. The branch point concentration was 3.9 × 10 ⁻⁶ mol / g, and the ether bond concentration was 0.8 × 10 ⁻⁶ mol / g. The melting point was 97.0 ° C.

[Production Example 6]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 40.00 kg of succinic acid containing 0.35% by weight of malic acid, 30.17 kg of 1,4-butanediol, 1.30 kg of ethylene glycol, ε -6.82 kg of caprolactone, 48.14 g of titanium tetraisopropoxide, and 9.84 g of magnesium hydrogen phosphate trihydrate were charged, and the temperature was gradually raised from room temperature to 240 ° C under a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.25 mol%. The esterification reaction was carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product was transferred to a high-viscosity batch-type polymerizer, stirred while maintaining the temperature of the reaction solution at 240 ° C. Finally, the polycondensation reaction was carried out by stirring for 7.5 hours at 1.0 mmHg (133 Pa). The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-like high molecular weight aliphatic polyester.
The aliphatic polyester had a weight average molecular weight of 210,000, a molecular weight distribution of 2.34, and an acid value of 1.2 mgKOH / g. The polymer copolymer composition was a butylene succinate unit of 82.8 mol%, an ethylene succinate unit of 4.6 mol%, and an ε-caprolactone unit of 12.6 mol%. 0.5 mol%, 1,4-butanediol residue 44.3 mol%, ethylene glycol residue 2.5 mol%, ε-caprolactone residue 6.7 mol%), and the hydroxyl group terminal concentration is 17.2 × 10 ^−6. Mol / g, branch point concentration was 6.0 × 10 ⁻⁶ mol / g, and ether bond concentration was 1.3 × 10 ⁻⁶ mol / g. The melting point was 94.5 ° C.

[Production Example 7]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 40.00 kg of succinic acid containing 0.35% by weight of malic acid, 33.58 kg of 1,4-butanediol, 4.30 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide and 6.05 g of magnesium acetate tetrahydrate were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the whole acid component at the time of preparation was 0.28 mol%. The esterification reaction is carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product is transferred to a high viscosity batch polymerization machine, the temperature of the reaction solution is kept at 240 ° C., and the pressure is gradually reduced from normal pressure. Finally, the polycondensation reaction was performed by stirring at 1.0 mmHg (133 Pa) for 5.5 hours. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
After the obtained pellet-like polymer was melted by feeding to an extruder at a flow rate of 7.4 kg / h by a quantitative feeder, a biaxial continuous polymerization reactor (glasses blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L) ) Continuously. Under a reduced pressure of 1.0 mmHg, the reaction solution was stirred at 6 rpm at a temperature of 245 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The polymer having a high molecular weight was continuously discharged from the reaction apparatus, and was cooled in a water tank and cut with a cutter to obtain a pellet-shaped high molecular weight aliphatic polyester.
The aliphatic polyester had a weight average molecular weight of 201,000, a molecular weight distribution of 2.31, and an acid value of 0.5 mgKOH / g. The polymer copolymer composition was 90.3 mol% of butylene succinate unit, 9.7 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 47.4 mol%, 1,4-butane Diol residue 47.5 mol%, ε-caprolactone residue 5.1 mol%), hydroxyl group terminal concentration 19.6 × 10 ⁻⁶ mol / g, branch point concentration 4.8 × 10 ⁻⁶ mol / g The ether bond concentration was 0.9 × 10 ⁻⁶ mol / g. The melting point was 103.2 ° C.

[Production Example 8]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 38.00 kg of succinic acid containing 0.35% by weight of malic acid, 30.45 kg of 1,4-butanediol, 12.24 kg of ε-caprolactone, 48.14 g of titanium tetraisopropoxide and 9.35 g of magnesium hydrogenphosphate trihydrate were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.23 mol%. The esterification reaction was carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product was transferred to a high viscosity batch polymerization machine, the temperature of the reaction solution was kept at 240 ° C., and the pressure was gradually reduced from normal pressure. Finally, the polycondensation reaction was carried out by stirring at 1.0 mmHg (133 Pa) for 4.5 hours. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
After the obtained pellet-like polymer was melted by feeding to an extruder at a flow rate of 7.4 kg / h by a quantitative feeder, a biaxial continuous polymerization reactor (glasses blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L) ) Continuously. Under a reduced pressure of 1.0 mmHg, the reaction solution was stirred at 6 rpm at a temperature of 245 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour. The polymer having a high molecular weight was continuously discharged from the reaction apparatus, and was cooled in a water tank and cut with a cutter to obtain a pellet-shaped high molecular weight aliphatic polyester.
The aliphatic polyester had a weight average molecular weight of 202,000, a molecular weight distribution of 2.32, and an acid value of 1.1 mgKOH / g. The polymer copolymer composition was 76.1 mol% of butylene succinate unit, 23.9 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 43.2 mol%, 1,4-butane Diol residue 43.2 mol%, ε-caprolactone residue 13.6 mol%), the hydroxyl group terminal concentration is 19.6 × 10 ⁻⁶ mol / g, and the branch point concentration is 5.3 × 10 ⁻⁶ mol / g. The ether bond concentration was 1.2 × 10 ⁻⁶ mol / g. The melting point was 85.0 ° C.

[Production Example 9]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 38.00 kg of succinic acid containing 0.35% by weight of malic acid, 30.45 kg of 1,4-butanediol, 12.24 kg of ε-caprolactone, 48.14 g of titanium tetraisopropoxide and 9.35 g of magnesium hydrogenphosphate trihydrate were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.23 mol%. The esterification reaction was carried out in the same manner as in Production Example 1, and the resulting aliphatic polyester low molecular weight product was transferred to a high-viscosity batch polymerization machine, the temperature of the reaction solution was kept at 245 ° C., and the pressure was gradually reduced from normal pressure. Finally, the polycondensation reaction was carried out by stirring at 1.0 mmHg (133 Pa) for 2.5 hours. After completion of the polycondensation reaction, 600 g of hexamethylene diisocyanate was added in a state where the temperature of the treatment liquid was adjusted to 190 ° C. and stirred, the viscosity increased rapidly, but gelation did not occur.
The obtained high molecular weight aliphatic polyester had a weight average molecular weight of 212,000, a molecular weight distribution of 2.35, and an acid value of 1.7 mgKOH / g. The polymer copolymer composition was 76.1 mol% of butylene succinate unit, 23.9 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 43.2 mol%, 1,4-butane Diol residue 43.2 mol%, ε-caprolactone residue 13.6 mol%), the hydroxyl group terminal concentration is 7.9 × 10 ⁻⁶ mol / g, and the branch point concentration is 3.8 × 10 ⁻⁶ mol / g. The ether bond concentration was 1.0 × 10 ⁻⁶ mol / g. The melting point was 85.0 ° C.

[Production Comparative Example 1]
After replacing the inside of a jacketed vertical reaction vessel equipped with paddle blades with nitrogen, 40.00 kg of succinic acid containing 0.88% by weight of malic acid, 33.58 kg of 1,4-butanediol, 9.67 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide and 4.92 g of magnesium hydrogenphosphate trihydrate were charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.62 mol%. In the same manner as in Production Example 2, an esterification reaction, a polycondensation reaction in a high-viscosity batch polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor are sequentially performed to obtain a pellet-like high molecular weight aliphatic polyester. It was.
Although the weight average molecular weight of the obtained high molecular weight aliphatic polyester was 219,000, the molecular weight distribution spread to 2.72. The acid value is 1.0 mg KOH / g, the polymer copolymer composition is 80.7 mol% of butylene succinate units, 19.3 mol% of ε-caprolactone units (when the structural unit derived from the raw material monomer is expressed as 100 mol%, succinic acid residue 44 0.6 mol%, 1,4-butanediol residue 44.7 mol%, ε-caprolactone residue 10.7 mol%), the hydroxyl group terminal concentration is 23.7 × 10 ⁻⁶ mol / g, and the branching point concentration is 10. 0.6 × 10 ⁻⁶ mol / g and the ether bond concentration was 2.8 × 10 ⁻⁶ mol / g. The melting point was 91.6 ° C.

[Production Comparative Example 2]
After replacing the inside of a jacketed vertical reactor equipped with paddle blades with nitrogen, 38.00 kg of succinic acid containing 0.88 wt% of malic acid, 30.45 kg of 1,4-butanediol, and 1 wt% of germanium oxide in advance. A dissolved 90% L-lactic acid aqueous solution of 3.85 kg was charged, and the temperature was gradually raised from room temperature to 240 ° C. in a nitrogen atmosphere. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.69 mol%. After starting the temperature increase, the reaction solution temperature reached 140 ° C. in 1.5 hours, and the distillation of water started. The esterification reaction was terminated when the amount of the distillate reached 11.3 kg in 5.0 hours after the start of temperature increase.
Subsequently, the resulting aliphatic polyester low molecular weight product was transferred to a high-viscosity batch polymerization machine, the temperature of the reaction solution was kept at 240 ° C., and gradually reduced from normal pressure to 1.0 mmHg (133 Pa). The polycondensation reaction was performed by stirring for 5.5 hours. The reaction product was discharged from the polymerization tank, cooled in a water tank, and cut with a cutter to obtain a pellet-shaped polymer.
After the obtained pellet-like polymer was melted by feeding to an extruder at a flow rate of 7.4 kg / h by a quantitative feeder, a biaxial continuous polymerization reactor (glasses blade polymerizer manufactured by Hitachi, Ltd., standard loading amount 6 L) ) Continuously. Under a reduced pressure of 1.0 mmHg, the mixture was stirred at 6 rpm at a reaction solution temperature of 240 ° C., and a polycondensation reaction was continuously performed with an average residence time of 1.0 hour.
The obtained aliphatic polyester had a weight average molecular weight as low as 188,000, a molecular weight distribution of 2.40, and an acid value of 1.9 mgKOH / g. The polymer copolymer composition was 93.3 mol% of butylene succinate units, 6.7 mol% of lactic acid units (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 47.9 mol%, 1,4-butanediol residue Group 48.6 mol%, lactic acid residue 3.5 mol%), hydroxyl group terminal concentration is 23.8 × 10 ⁻⁶ mol / g, branch point concentration is 12.2 × 10 ⁻⁶ mol / g, ether bond concentration Was 12.2 × 10 ⁻⁶ mol / g. The melting point was 106.1 ° C.

[Production Example 10] (Production of Resin 1)
3. Succinic acid 43.18 kg containing malic acid 0.47 wt% (0.41 mol%), 1,4-butanediol 34.60 kg, titanium tetraisopropoxide 24.07 g, magnesium hydrogen phosphate trihydrate 92 g was charged, and in the same manner as in Production Example 1, an esterification reaction, a polycondensation reaction in a high-viscosity batch-type polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor were sequentially performed, and a pellet-like high molecular weight fat was obtained. A group polyester was obtained.
The obtained high molecular weight aliphatic polyester (polybutylene succinate) had a weight average molecular weight of 242,000, a molecular weight distribution of 1.94, and an acid value of 0.9 mgKOH / g. When the structural unit derived from the raw material monomer was expressed as 100 mol%, it was 49.4 mol% succinic acid residue and 50.6 mol% 1,4-butanediol residue. The hydroxyl terminal concentration was 16.6 × 10 ⁻⁶ mol / g, the branching point concentration was 7.8 × 10 ⁻⁶ mol / g, and the ether bond concentration was 0.9 × 10 ⁻⁶ mol / g. The melting point was 114.2 ° C.

[Production Example 11] (Production of Resin 2)
35.07 kg of succinic acid containing 0.35% by weight of malic acid, 10.04 kg of adipic acid, 34.60 kg of 1,4-butanediol, 24.07 g of titanium tetraisopropoxide, magnesium hydrogenphosphate trihydrate 92 g was charged, and in the same manner as in Production Example 1, an esterification reaction, a polycondensation reaction in a high-viscosity batch-type polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor were sequentially performed, and a pellet-like high molecular weight fat was obtained. A group polyester was obtained. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.25 mol%.
The obtained high molecular weight aliphatic polyester had a weight average molecular weight of 268,000, a molecular weight distribution of 1.97, and an acid value of 1.1 mgKOH / g. The polymer copolymer composition was 81.2 mol% of butylene succinate unit, 18.8 mol% of butylene adipate unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 40.3 mol%, adipic acid residue 9. 3 mol%, 1,4-butanediol residue 50.4 mol%), the hydroxyl group terminal concentration is 11.7 × 10 ⁻⁶ mol / g, the branching point concentration is 4.6 × 10 ⁻⁶ mol / g, ether The binding concentration was 0.5 × 10 ⁻⁶ mol / g. The melting point was 92.3 ° C.

[Production Example 12] (Production of Resin 3)
40.00 kg of succinic acid containing 0.11% by weight of malic acid, 32.05 kg of 1,4-butanediol, 8.70 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide, magnesium hydrogenphosphate trihydrate 4 .92 g were charged, and in the same manner as in Production Example 2, an esterification reaction, a polycondensation reaction in a high-viscosity batch polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor were sequentially performed, and a high molecular weight in the form of pellets An aliphatic polyester was obtained. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.08 mol%.
The obtained high molecular weight aliphatic polyester had a weight average molecular weight of 231,000, a molecular weight distribution of 1.99, and an acid value of 0.9 mgKOH / g. The polymer copolymer composition was a butylene succinate unit of 82.8 mol% and an ε-caprolactone unit of 17.2 mol%. Diol residue 45.6 mol%, ε-caprolactone residue 9.3 mol%), hydroxyl group terminal concentration is 10.5 × 10 ⁻⁶ mol / g, and branch point concentration is 0.8 × 10 ⁻⁶ mol / g. The ether bond concentration was 0.5 × 10 ⁻⁶ mol / g. The melting point was 94.6 ° C.

[Production Example 13] (Production of Resin 4)
40.00 kg of succinic acid containing 0.35% by weight of malic acid, 32.05 kg of 1,4-butanediol, 8.70 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide, magnesium hydrogen phosphate trihydrate 4 .92 g was charged, and in the same manner as in Production Example 9, an esterification reaction, a polycondensation reaction in a high-viscosity batch type polymerizer, and a linking reaction by adding a linking agent were sequentially performed to obtain a pellet-shaped high molecular weight aliphatic polyester. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.25 mol%.
The obtained high molecular weight aliphatic polyester had a weight average molecular weight of 228,000, a molecular weight distribution of 2.24, and an acid value of 1.0 mgKOH / g. The polymer copolymer composition was a butylene succinate unit of 82.8 mol%, an ε-caprolactone unit of 17.2 mol% (when the structural unit derived from the raw material monomer was expressed as 100 mol%, the succinic acid residue was 45.0 mol%, and 1,4-butane Diol residue 45.6 mol%, ε-caprolactone residue 9.4 mol%), the hydroxyl group terminal concentration is 13.2 × 10 ⁻⁶ mol / g, and the branching point concentration is 4.6 × 10 ⁻⁶ mol / g. The ether bond concentration was 0.2 × 10 ⁻⁶ mol / g. The melting point was 94.6 ° C.

[Production Comparative Example 3] (Production of Resin 5)
40.00 kg of succinic acid containing 0.91% by weight of malic acid, 32.05 kg of 1,4-butanediol, 8.26 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide, magnesium hydrogen phosphate trihydrate 4 .92 g were charged, and in the same manner as in Production Example 2, an esterification reaction, a polycondensation reaction in a high-viscosity batch polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor were sequentially performed, and a high molecular weight in the form of pellets An aliphatic polyester was obtained. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.66 mol%.
Although the weight average molecular weight of the obtained high molecular weight aliphatic polyester was 262,000, the molecular weight distribution spread to 2.75. The polymer copolymer composition was 83.5 mol% of butylene succinate unit, 16.5 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 45.2 mol%, 1,4-butane Diol residue 45.9 mol%, ε-caprolactone residue 8.9 mol%), acid value is 0.9 mgKOH / g, hydroxyl group terminal concentration is 21.1 × 10 ⁻⁶ mol / g, branching point concentration is 11 0.2 × 10 ⁻⁶ mol / g and ether bond concentration was 0.1 × 10 ⁻⁶ mol / g. The melting point was 95.4 ° C.

[Production Comparative Example 4] (Production of Resin 6)
40.00 kg of succinic acid containing 0.91% by weight of malic acid, 32.05 kg of 1,4-butanediol, 8.26 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide, magnesium hydrogen phosphate trihydrate 4 .92 g was charged, and in the same manner as in Production Example 9, an esterification reaction, a polycondensation reaction in a high-viscosity batch type polymerizer, and a linking reaction by adding a linking agent were sequentially performed to obtain a pellet-shaped high molecular weight aliphatic polyester. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.66 mol%.
Although the weight average molecular weight of the obtained high molecular weight aliphatic polyester was 266,000, the molecular weight distribution spread to 2.93. The polymer copolymer composition was 83.5 mol% of butylene succinate unit, 16.5 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 45.1 mol%, 1,4-butane Diol residue 46.0 mol%, ε-caprolactone residue 8.9 mol%), acid value is 1.0 mgKOH / g, hydroxyl group terminal concentration is 21.5 × 10 ⁻⁶ mol / g, branching point concentration is 11 .5 × ¹⁰ -6 mol / g, an ether bond concentration was 0.7 × ¹⁰ -6 mol / g. The melting point was 95.4 ° C.

[Production Comparative Example 5] (Production of Resin 7)
40.00 kg of succinic acid containing 0.77% by weight of malic acid, 32.05 kg of 1,4-butanediol, 3.04 kg of ε-caprolactone, 24.07 g of titanium tetraisopropoxide, magnesium hydrogen phosphate trihydrate 4 .92 g were charged, and in the same manner as in Production Example 2, an esterification reaction, a polycondensation reaction in a high-viscosity batch polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor were sequentially performed, and a high molecular weight in the form of pellets An aliphatic polyester was obtained. The malic acid concentration with respect to the entire acid component at the time of preparation was 0.63 mol%.
Although the weight average molecular weight of the obtained high molecular weight aliphatic polyester was 230,000, the molecular weight distribution spread to 2.72. The polymer copolymer composition was 93.2 mol% of butylene succinate unit, 6.8 mol% of ε-caprolactone unit (when the structural unit derived from the raw material monomer was expressed as 100 mol%, succinic acid residue 47.9 mol%, 1,4-butane Diol residue 48.6 mol%, ε-caprolactone residue 3.5 mol%), acid value is 1.0 mg KOH / g, hydroxyl group terminal concentration is 20.3 × 10 ⁻⁶ mol / g, and branch point concentration is 10 0.8 × 10 ⁻⁶ mol / g and the ether bond concentration was 1.1 × 10 ⁻⁶ mol / g. The melting point was 106.1 ° C.

[Production Comparative Example 6] (Production of Resin 8)
Comparative Example of Production: 38.00 Kg of succinic acid containing 0.77% by weight of malic acid, 30.45 Kg of 1,4-butanediol, and 2.07 Kg of 90% L-lactic acid aqueous solution in which 1% by weight of germanium oxide was dissolved in advance. In the same manner as in No. 2, an esterification reaction, a polycondensation reaction in a high-viscosity batch polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reactor were sequentially performed to obtain a pellet-like high molecular weight aliphatic polyester. The malic acid concentration with respect to the whole acid component at the time of preparation was 0.64 mol%.
The resulting aliphatic polyester had a weight average molecular weight as low as 189,000, a molecular weight distribution of 2.63, and an acid value of 1.8 mgKOH / g. The polymer copolymer composition is 95.8 mol% of butylene succinate units, 4.2 mol% of lactic acid units (when the structural unit derived from the raw material monomer is expressed as 100 mol%, succinic acid residue 49.0 mol%, 1,4-butanediol residue Group 48.9 mol%, lactic acid residue 2.1 mol%), hydroxyl terminal concentration is 14.3 × 10 ⁻⁶ mol / g, branch point concentration is 12.0 × 10 ⁻⁶ mol / g, ether bond concentration Was 12.1 × 10 ⁻⁶ mol / g. The melting point was 108.5 ° C.

[Production Comparative Example 7] (Production of Resin 9)
29.96 kg of succinic acid containing 0.97 wt% of malic acid, 9.91 kg of adipic acid, 30.45 kg of 1,4-butanediol, and 2.07 kg of 90% L-lactic acid aqueous solution in which 1 wt% of germanium oxide is dissolved in advance. In the same manner as in Production Comparative Example 2, an esterification reaction, a polycondensation reaction in a high-viscosity batch-type polymerization machine, and a continuous polycondensation reaction in a biaxial continuous polymerization reaction apparatus were sequentially performed, and a pellet-like high molecular weight aliphatic was obtained. Polyester was obtained. The malic acid concentration with respect to the whole acid component at the time of preparation was 0.64 mol%.
The resulting aliphatic polyester had a low weight average molecular weight of 181,000, a molecular weight distribution of 2.38, and an acid value of 1.7 mgKOH / g. The polymer copolymer composition is 75.6 mol% of butylene succinate unit, 20.2 mol% of butylene adipate unit, 4.2 mol% of lactic acid unit (when the structural unit derived from the raw material monomer is expressed as 100 mol%, the succinic acid residue is 38.7 mol%. Adipic acid residue 10.3 mol%, 1,4-butanediol residue 48.8 mol%, lactic acid residue 2.2 mol%), and the hydroxyl group terminal concentration is 13.5 × 10 ⁻⁶ mol / g, branched. The point concentration was 12.0 × 10 ⁻⁶ mol / g, and the ether bond concentration was 10.9 × 10 ⁻⁶ mol / g. The melting point was 84.3 ° C. Table 1 shows analysis values and physical property values of the resins 1 to 9 obtained above.

  Next, the molded product of the low-branching high molecular weight aliphatic polyester composition of the present invention will be specifically described with reference to Examples, but the molded product of the present invention is not limited thereto. The resins 1 to 9 were subjected to various moldings and various measurements under the following conditions.

Film forming: A film was obtained under the following conditions using the following extruder and blown film forming machine.
(I) Extruder specifications Screw diameter: 40 mm, uniaxial cylinder L / D: 28
Die diameter: 50mmφ
Die lip opening: 2.5mm
(Ii) Extrusion conditions Screw rotation speed: 50 rpm
Extruder cylinder set temperature: 170 ° C
Blow ratio (TD stretch ratio): 4.0 times MD stretch ratio: 31 times (film thickness 20 μm) and 15.5 times (film thickness 40 μm)
Take-off speed: 17.0 (film thickness 20 μm) and 8.5 m / min (film thickness 40 μm)

Various measurement methods used below in the present invention are as follows.
(6) Tensile test Based on JIS K6781, the tensile elastic modulus (MPa) and elongation (% (GL reference | standard)) of the test piece were calculated | required. The test piece was a tensile test piece of the same standard, and the tensile test was performed at a crosshead speed of 500 mm / min. Equipment used: Tensilon universal testing machine UCT-5 manufactured by Orientec. The measured value is an average value of 20 times.

(7) High speed tensile test (Daicel method)
The high-speed tensile test was performed using the following film test piece and a high-speed tensile test apparatus as exemplified in FIG. 6, and the tensile elongation at the time of breaking the film test piece was measured.
Film test piece: As the test piece, a tensile test piece defined in JIS K6781 was used. The distance between the marked lines of this test piece is 40 mm.
Test apparatus: The test apparatus used for this high-speed tensile test is a high-speed tensile test apparatus capable of extending the film test piece in one direction at a constant speed. The high-speed tensile test apparatus has two chucks capable of fixing a film test piece, one of the chucks is fixed, and the other chuck is moved at a constant speed of 50 mm / second to 1000 mm / second to move the film. Can stretch.
In the high-speed tensile test apparatus as illustrated in FIG. 6, a fixed end (2) having a chuck (21, 41) for fixing a film test piece on a flat test stand (5) and a non-extensible connecting piece ( 4) are arranged on a straight line. The moving end chuck (41) provided on the non-extensible connecting piece (4) is wound at a constant speed within the above range by the winding device (3) winding up the film-like non-extensible connecting band (42). Move in the direction of the winding device. The maximum distance between the fixed end chuck (21) and the moving end chuck (41) is 600 mm.
When starting the test, the film test piece was fixed at one end to the chuck (21) of the fixed end (2) and at the other end to the moving end chuck (41) so that there was no distortion in the winding direction. Thereafter, the winding device (3) was operated, the moving end chuck (41) was moved at a constant speed, and the film test piece was stretched (high-speed tensile test). The test was terminated when the film specimen broke or when the distance between chucks reached the maximum distance.
The state from the start to the end of the test was photographed over time by the image capturing device (6), the time from the start to the end of the test was measured from the obtained moving image, and the required time and the moving end chuck (41 ) To calculate the moving distance of the moving end chuck (41) when the film test piece is broken, and the value obtained by dividing the moving distance by the distance between the marked lines of the film test piece is the tensile breaking elongation in this test. (%). Other test conditions are as follows.
Test atmosphere: room temperature 23 ° C, humidity 50% RH
Distance between chucks: 8cm
Test speed: 100 mm / sec Tensile condition: Constant speed tensile Test number: The average value and standard deviation of the elongation at break obtained by the measurement of 20 repetitions were calculated, and the fluctuation rate [(standard deviation / average value) × 100 (%)].

(8) Falling ball impact test Number of test pieces when the film was fixed to a circular frame with a diameter of 12 cm and the following balls were dropped using an electromagnet-type weight releasing device in an atmosphere of 23 ° C. and 50% RH. Measure the drop height H (d) of the sphere when 50% of the rupture is broken (where d is the film thickness (μm)). The number of repeated tests n = 20.
Falling ball (I) Φ41mm, mass 286g.
Falling ball (b) Φ19 mm, mass 28 g.
In the following embodiment, it is displayed as “falling ball height (cm)”.

(9) Heat shrinkage stress A film-shaped test piece having a predetermined thickness is cut into a strip shape having a width of 1 cm and a length of 10 cm, and a plurality of sheets are stacked so that the total thickness is in the range of 100 to 200 μm. Using a tensile viscometer manufactured by Toyo Seiki Co., Ltd., the stress generated between the chucks was measured when immersed in an oil bath at 125 ° C. with a distance between chucks of 10 cm. This is the heat shrinkage stress.

(10) Drop weight impact test According to ASTM D3763. Using a press-molded plate with a thickness of 1.5 mm, measure the load-strain curve by the surface impact drop impact test, the region up to the yield point as the elastic deformation region, and the region from the yield point to the break point as the propagation region Elastic deformation energy Ep (unit: J) and propagation energy Eg (unit: J) were determined.
Press molding plate forming conditions: The resin was preheated at 190 ° C. for 5 minutes, then pressed at the same temperature for 5 minutes under 10 MPa pressure, and then cooled at 20 ° C. under 10 MPa pressure for 3 minutes.
Sample shape: 100mm x 100mm x 1.5mm
Instrumented drop weight impact tester (Fig. 1): Graphic impact tester manufactured by Toyo Seiki Co., Ltd. (impact end diameter of the striker with load cell 12.7mm, sample holder diameter 76mm, drop weight weight 6.5kgf, drop weight height 80cm)
FIG. 2 is an example of a load-strain curve of a press-formed plate obtained by a drop weight impact test. In FIG. 2, the region from the start point (load 0) to the yield point (maximum load value) is the elastic deformation region, and the region from the yield point to the break point (load 0) is the propagation region.
The ductility ratio is a ratio Eg / (Eg + Ep) between the energy Ep (unit: J) in the elastic deformation region and the energy Eg (unit: J) in the propagation region.

(11) Charpy impact test (Daicel method)
Except for the sample and its fixing method, it conformed to the Charpy impact test method of JIS K7111.
Film specimen: Dumbbell-shaped tensile specimen in accordance with JIS K6781. At this time, the longitudinal direction of the dumbbell parallel part is matched with the TD direction of the film. Equipment used: Impact tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. FIG. In FIG. 2, the film sample is fixed by a pair of fixing jigs 1. The fixing jig 1 sandwiches and fixes the film-like sample by rotating the bolt part 2 using a wrench or the like. The tightening strength is set so that no slip occurs between the film sample and the fixing jig 1 during the test.
Hold the film sample so that the distance between the gripping jigs is 40 mm and the center of the parallel part of the sample's dumbbell is perpendicular to the impact blade at the center of the impact blade attached to the impact tester. Adjusted the height and position of the tool.
The energy loss of the hammer due to sample breakage was measured under the conditions of a hammer mass of 90 kgf and an impact speed of 2.9 m / sec. Repeat 20 times. The average value and the standard deviation of the measured values were calculated, and the fluctuation rate = (standard deviation / average value) × 100 was obtained.

[Examples I-1 to I-4, Comparative Examples I-1 to I-5]
Using a resin 1-9, a compression molded product having a thickness of 1.5 mm was subjected to a falling impact test based on ASTM D3763, and the elastic deformation energy Ep (unit: J) to the yield point and propagation from the yield point to the fracture point The energy Eg (unit: J) was measured to determine the ductility ratio Eg / (Eg + Ep). The results are summarized in Table 2.

Hereinafter, the high impact-resistant film using the high molecular weight aliphatic polyester composition of the present invention will be described with reference to examples.
[Examples II-1 to II-2, Comparative Examples II-1 to II-2]
Using the resin shown in Table 3 obtained in the production example, a film having a thickness of about 20 μm was obtained at a film take-off speed of 17.0 m / min using an inflation molding machine.
[Example II-3, Comparative Example II-3]
Using the resin shown in Table 3 obtained in the production example, a film (Example II-3) having a thickness of about 40 μm at a film take-off speed of 8.5 m / min using an inflation molding machine was 34.0 m. A film (Comparative Example II-3) having a thickness of about 20 μm at a rate of 1 min was obtained. The composition and physical properties of the above film are summarized in Table 3.

It is a figure which shows the outline | summary of the falling weight impact test of a compression molded product. It is an example of the load-strain curve obtained by the falling weight impact test. It is a figure which shows an example of the film-form sample fixing device in a Charpy impact test. It is an example of the ¹ H-NMR spectrum of the low-branching high molecular weight aliphatic polyester of the present invention. It is an example of the GPC elution curve of the low branching high molecular weight aliphatic polyester of this invention. It is an example of the conceptual diagram of the test apparatus used for a high-speed tensile test.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Test piece 2 Fixed end 21 Fixed end chuck 3 Winding device 31 Rotating roll 32 Motor 33 Winding string 4 Non-extensible connecting piece 41 Moving end chuck 42 Non-extensible connecting band 5 Test stand 6 Image taking device

Claims (18)

The molecular chain is a structural unit represented by the following general formulas (1) and (2) (the amount of the structural unit represented by (1) and (2) is substantially equimolar),
—CO—R ¹ —CO— (1)
(In the formula, R ¹ represents a C 1-12 divalent aliphatic group.)
—O—R ² —O— (2)
(Wherein R ² represents a divalent aliphatic group having 2 to 12 carbon atoms), and a structural unit represented by the following general formula (3) —CO—R ³ —O— (3)
(In the formula, R ³ represents a divalent aliphatic group having 1 to 10 carbon atoms.)
A low-branching high molecular weight aliphatic polyester consisting of
100-75 mol% of 100 mol% of the structural units represented by the general formula (1) is a succinic acid residue,
The molar fraction of the structural unit amount represented by the general formula (3) to the sum of the structural unit amounts represented by the general formulas (1) and (3) is 0 to 0.25,
The weight average molecular weight (Mw) is 180,000 or more,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.7 or less,
CH group by ¹ H-NMR measurement of a branched structure represented by the following formula (4):
—O—C (═O) —CH (O—C (═O) —) CH ₂ —C (═O) O— (4)
A low-branching high molecular weight aliphatic polyester having a content of 10 × 10 ⁻⁶ mol / g or less.   The low-branching high molecular weight aliphatic polyester according to claim 1, having an acid value of 2.0 mgKOH / g or less. The low-branching high molecular weight aliphatic polyester according to claim 1 or 2, wherein the hydroxyl group terminal concentration by ¹ H-NMR measurement is 40 x 10 ^-6 mol / g or less. ^4. The low-branching high-molecular-weight aliphatic polyester according to claim 1, wherein the ether bond concentration by ¹ H-NMR measurement is 7.0 × 10 ⁻⁶ mol / g or less.   The low structural unit according to any one of claims 1 to 4, wherein 100 to 75 mol% of the structural unit represented by the general formula (1) is a succinic acid residue, and the remaining 0 to 25 mol% is an adipic acid residue. Branched high molecular weight aliphatic polyester.   The low-branching high molecular weight aliphatic polyester according to any one of claims 1 to 5, wherein the structural unit represented by the general formula (2) is an ethylene glycol residue and / or a 1,4-butanediol residue. .   The structural unit represented by the general formula (3) is ε-caprolactone, 4-methyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone, 3,5,5-trimethyl-ε-caprolactone, β- The residue based on at least one selected from the group consisting of propiolactone, γ-butyrolactone, δ-valerolactone, enanthlactone, glycolic acid, lactic acid, and 3-hydroxybutyric acid. 2. The low-branching high molecular weight aliphatic polyester according to item 1.   The molar fraction of the structural unit amount represented by the general formula (3) with respect to the total amount of the structural units represented by the general formulas (1) and (3) is 0.04 to 0.25. The low branching high molecular weight aliphatic polyester according to any one of the above.   Low-branched high molecular weight aliphatic polyesters are polybutylene succinate, poly (butylene succinate-butylene adipate) copolymer, poly (butylene succinate-ε-caprolactone) copolymer, poly (butylene succinate-lactic acid) The low-branching high molecular weight aliphatic polyester according to any one of claims 1 to 8, which is a copolymer, a poly (butylene succinate-butylene adipate-lactic acid) copolymer, and / or a polyethylene succinate.   A low-branched high molecular weight aliphatic polyester molded product obtained by molding the low-branched high molecular weight aliphatic polyester according to any one of claims 1 to 9.   Molding is extrusion molding, injection molding, compression molding, injection compression molding, transfer molding, casting molding, stampable molding, blow molding, stretched film molding, inflation film molding, laminate molding, calendar molding, foam molding, RIM molding, FRP The low-branched high molecular weight aliphatic polyester molded article according to claim 10, which is molded, powder molded or paste molded.   An elastic deformation energy Ep (unit: J) up to the yield point in the strain-stress curve and a propagation energy Eg from the yield point to the fracture point in a strain-stress curve of a compression molded product having a thickness of 1.5 mm by a drop impact test based on ASTM D3763 The low branched high molecular weight aliphatic polyester molded article according to claim 10 or 11, wherein the total absorbed energy Eg + Ep (unit: J) is 10 J or more when the unit: J) is measured.   The low branching high molecular weight aliphatic polyester molded article according to claim 12, wherein the propagation energy Eg is 5.5 J or more.   The low-branching high molecular weight aliphatic polyester molded article according to any one of claims 10 to 13 is a film having a thickness of 5 µm to 0.5 mm, and is a non-stretched or uniaxially or biaxially stretched low Branched high molecular weight aliphatic polyester film.   The low-branching high-molecular-weight aliphatic polyester according to claim 14, wherein a falling ball impact test height H (d = thickness) using a sphere having a diameter of 19 mm and a weight of 28 g is 20 cm or more when converted to a film thickness of 20 μm. the film.   The low-branching high molecular weight according to claim 14 or 15, wherein a thermal shrinkage stress (SMD) in the MD direction is 0.4 MPa or less and a ratio SMD / STD to a thermal shrinkage stress (STD) in the TD direction is 10 or less. Aliphatic polyester film.   The low value according to any one of claims 14 to 16, wherein an average value of elongation at break is 750% or more and a variation rate thereof is 15% or less by a high-speed tensile test (Daicel method) in a TD direction of the film. Branched high molecular weight aliphatic polyester film. The low branching degree high according to any one of claims 14 to 17, wherein an average value of absorbed energy is 150 MPa or more and a variation rate thereof is 50% or less by a Charpy impact test (Daicel method) in a TD direction of the film. Molecular weight aliphatic polyester film.

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