JP2006213828A - Polyester containing polylactic acid component segment and its manufacturing method - Google Patents

Polyester containing polylactic acid component segment and its manufacturing method Download PDF

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JP2006213828A
JP2006213828A JP2005028420A JP2005028420A JP2006213828A JP 2006213828 A JP2006213828 A JP 2006213828A JP 2005028420 A JP2005028420 A JP 2005028420A JP 2005028420 A JP2005028420 A JP 2005028420A JP 2006213828 A JP2006213828 A JP 2006213828A
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polylactic acid
segment
component
acid component
residue
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JP2006213828A5 (en
JP4665540B2 (en
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Masahiro Kimura
Hiroshige Matsumoto
Jun Sakamoto
純 坂本
将弘 木村
太成 松本
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Toray Ind Inc
東レ株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystalline polylactic acid resin composition excellent in heat resistance and mechanical properties; and a film made thereof. <P>SOLUTION: The polyester containing a polylactic acid component segment at least comprises a segment (I) consisting of a polylactic acid component having crystallinity and a segment (II) consisting of an aromatic polyester component, the weight ratio of the segment (I)/the segment (II) being (5/95)-(70/30). This polyester containing the polylactic acid component segment is used as a modifier for lactic acid. The crystalline polylactic acid resin composition contains the polyester containing the polylactic acid component segment. The film is made of this composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polylactic acid component segment-containing polyester and a method for producing the same, and more particularly to a crystalline polylactic acid resin composition and film containing these polyesters, having high heat resistance and excellent mechanical properties.

  Polylactic acid has a high melting point and is expected to be a practically excellent biodegradable polymer that can be melt-molded. For example, polylactic acid film is said to have the highest tensile strength and elastic modulus among various biodegradable films, and is excellent in gloss and transparency, but this temperature is relatively low because the glass transition temperature of the resin is relatively low. There has been a problem that heat deformation and rigidity reduction are large and heat resistance is inferior to that of general-purpose polymers. (For example, refer nonpatent literature 1).

As a method for solving this problem, a resin having a glass transition temperature higher than that of polylactic acid is blended. However, since both are incompatible with each other, the effect is not sufficient, and There was a problem that a transparent film could not be obtained. On the other hand, as a method of mixing a resin having compatibility with polylactic acid, non-patent documents 2, 3 and the like are mixed with polymethylmethacrylate having a glass transition temperature of about 100 ° C., so that the glass of the resin composition is mixed. It is described that the transition temperature is improved, and in Patent Document 1, an aromatic polyester and polylactic acid are mixed and made into a compatible state, then solidified and pulverized and then solid-phase polymerized to obtain a block copolymer. Patent Document 2 describes a block polymer composed of terephthalic acid ester and polylactic acid. However, the methods of Patent Document 1 and Patent Document 2 are disadvantageous in terms of cost because it is necessary to make a completely new polymer according to the required characteristics.
Mochizuki Masaaki et al., "Biodegradable Chemicals and Plastics", CMC Corporation, 2000, p147 Polymer 39 (26), p6891 (1998) Macromol.Chem.Phys. 201, p.1295 (2000) JP 2002-338673 A JP 2004-285454 A

  An object of the present invention is to provide a crystalline polylactic acid resin composition containing a polylactic acid component segment-containing polyester excellent in heat resistance, mechanical properties, and hydrolysis resistance, and a film containing the same, at low cost.

  The object of the present invention described above includes a segment (I) composed of a polylactic acid component having crystallinity and a segment (II) composed of an aromatic polyester component, and the weight ratio (I) of the segments (I) and (II). / (II) is achieved by a polylactic acid component segment-containing polyester having a ratio of 5/95 to 70/30.

  According to the present invention, a crystalline polylactic acid resin composition or film excellent in heat resistance, mechanical properties, and hydrolysis resistance can be obtained at low cost.

In the crystalline polylactic acid resin composition of the present invention, a polylactic acid component segment-containing polyester (hereinafter sometimes referred to as “polylactic acid modifier” or simply “modifier”) is added to various polylactic acid resins. The crystalline polylactic acid resin composition having various characteristics can be obtained by changing the type and amount of the polylactic acid modifier. It is not necessary to individually polymerize a polylactic acid resin having a specific composition in advance, and a crystalline polylactic acid resin composition having various characteristics can be produced at a low cost.

It is important that the modifier for polylactic acid in the present invention comprises at least a segment (I) composed of a polylactic acid component having crystallinity and a segment (II) composed of an aromatic polyester component. When the polylactic acid modifier of the present invention is added to the crystalline polylactic acid, the segment (I) is incorporated into the crystal made of the crystalline polylactic acid as the matrix resin (hereinafter referred to as “co-crystallization”). To improve the properties of the crystalline polylactic acid resin composition. Therefore, it is important that the segment (I) is composed of at least a polylactic acid component having crystallinity. The segment (I) may be L-form, D-form or a mixture thereof, but is preferably mainly composed of L-form.
In order to impart heat resistance to the crystalline polylactic acid resin composition, it is important to combine the segment (II) composed of the aromatic polyester component. This is presumed that the crystalline polylactic acid partial segment (I) part forms a co-crystallized structure with the polylactic acid resin, and the aromatic polyester component is connected between them to improve the heat resistance.

  In order to improve the heat resistance and mechanical properties of the polylactic acid resin, it is important that the weight ratio (I) / (II) of the segments (I) and (II) is 5/95 to 70/30. When the weight ratio is less than 5/95, since the segment (I) component is small, it becomes difficult to form a co-crystallized structure with the polylactic acid resin, and the effect of improving the characteristics becomes small. Moreover, when this weight ratio exceeds 70/30, since an aromatic polyester segment (II) component decreases, the characteristic improvement effect becomes small. A more preferred weight ratio is 10/90 to 60/40.

  The polylactic acid modifier of the present invention preferably has a number average molecular weight of 28,000 or less from the viewpoint of compatibility with the polylactic acid resin and the crystallinity. When the number average molecular weight exceeds 28,000, the compatibility with the polylactic acid resin may be inferior. More preferably, it is the range of 1,000-25,000. If it is the modifier for polylactic acid which has the number average molecular weight of such a range, the characteristic of a crystalline polylactic acid resin composition will become favorable.

  In the modifier for polylactic acid of the present invention, the aromatic polyester segment (II) is preferably a component having a high glass transition temperature Tg and / or a melting point Tm. As such components, divalent naphthalene residue, phenylene residue, divalent cyclohexane residue, spiroglycol residue, fluorene residue, isosorbate residue, phenylindane residue, diphenylsulfone residue, biphenyl residue Imide residues and the like, and the aromatic polyester segment (II) preferably contains at least one component selected from these. In addition, although what is not aromatic is also contained in the said component, in that case, what is necessary is just to contain at least 1 type of another aromatic type structure.

  The polylactic acid modifier of the present invention is preferably an ABA type or AB type block copolymer, where A is the component of segment (I) and B is the component of segment (II). Although the AB random body also contributes to the improvement of the characteristics of the polylactic acid resin, the block type is preferred because it is difficult to form a co-crystallized structure with the polylactic acid resin.

  Moreover, it is preferable that the carboxyl group terminal of the modifier for polylactic acid of this invention is 50 equivalent / t or less. When this value exceeds 50 equivalent / t, the heat resistance and hydrolysis resistance of the polylactic acid resin composition containing the same are likely to deteriorate.

  The method for producing the polylactic acid modifier of the present invention is not particularly limited, but the aromatic polyester is esterified or transesterified from dicarboxylic acid and / or its ester-forming derivative and diol and / or its ester-forming derivative. Produced by a process comprising at least a process B for removing a free diol component from an aromatic polyester, a process C for dissolving ring-opening polymerization after dissolving the aromatic polyester and lactide from which the free diol component has been removed. It is preferable to do. The polylactic acid modifier produced by such a production method is easy to produce an ABA type or AB type block polymer, has few unreacted segment (I) and segment (II) components, and has characteristics of polylactic acid resin. It becomes a preferable modifier for improvement.

As specific examples, the case where the raw materials are dimethyl naphthalenedicarboxylate and ethylene glycol will be described below.
In step A, dimethyl naphthalenedicarboxylate and a 2-fold molar amount of ethylene glycol are charged into a reaction vessel, and about 0.05% by weight of magnesium acetate is added to dimethyl naphthalenedicarboxylate and dissolved at 180 ° C. When the dissolution is completed, the temperature is raised while distilling methanol up to 235 ° C. while stirring the reaction vessel. When methanol distillation is completed, the reaction product is taken out, cooled, solidified, and pulverized. In step B, the reactant is dissolved in hexafluoroisopropanol, and the solution is dropped into a large amount of water. Polyethylene naphthalate low polymer precipitates in water, but free ethylene glycol dissolved in the low polymer dissolves in water. The polyethylene naphthalate low polymer precipitated in water is recovered by filtration or centrifugation and washed with water. By repeating this several times, a polyethylene naphthalate low polymer containing no free ethylene glycol can be obtained. Subsequently, the polyethylene naphthalate low polymer is dried under reduced pressure to remove moisture. In Step C, L-lactide and the polyethylene naphthalate low polymer obtained in Step B are charged in a predetermined amount into a reaction vessel, and melted and dissolved at about 140 ° C. When a uniform melt is obtained, tin 2-ethylhexanoate is added in an amount of about 0.1% by weight based on L-lactide. After adding tin 2-ethylhexanoate and reacting for 1 hour, chloroform is added and the reaction product is dissolved. Methanol containing hydrochloric acid is prepared in an amount 10 times that of chloroform, and a chloroform solution is slowly added to the methanol to precipitate the reaction product. The precipitate is separated by filtration, then dissolved again in chloroform, and precipitated again by adding to methanol. In this way, an ABA type block polymer (polylactic acid modifier) composed of crystalline polylactic acid segment (I) and aromatic polyester segment (II) can be obtained.
Further, the process D for depolymerizing an already high molecular weight aromatic polyester with a diol may be produced in place of the process A, and the molded article molded as the aromatic polyester at this time Can also be used. In particular, it is preferable to use recovered materials such as bottles, fibers and films because the quality of the aromatic polyester is high.

  The obtained polylactic acid modifier is used by adding to a crystalline polylactic acid resin. The crystalline polylactic acid resin is not particularly limited as long as it exhibits a melting peak by DSC measurement, and it is preferable that the L-form is contained in an amount of 80 mol% or more or the D-form is contained in an amount of 80 mol% or more as the lactic acid component. Is preferably 90 mol% or more, or more preferably 90 mol% or more of D form, more preferably 95 mol% or more of L form, or 95 mol% or more of D form.

The melting point of the crystalline polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher. The melting point of the crystalline polylactic acid resin is usually increased by increasing the optical purity of the lactic acid component, and the crystalline polylactic acid resin having a melting point of 120 ° C. or higher contains 90 mol% or more of the L form or the D form. Is contained in an amount of 90 mol% or more, and a crystalline polylactic acid resin having a melting point of 150 ° C. or more can be obtained by containing 95 mol% or more of L form or 95 mol% or more of D form. .
The melting point of polylactic acid is about 170 ° C. even when the L isomer is 99 mol% or more or the D isomer is 99 mol% or more, that is, the optical purity is 98% or more. A so-called stereocomplex crystal in which a crystal is formed by pairing (for example, poly L-lactic acid and poly D-lactic acid) shows a melting point of around 220 to 230 ° C. Therefore, when a melting point higher than 170 ° C. is desired, for example, poly L-lactic acid and poly D-lactic acid each having an optical purity of 95% or more may be used in combination as the crystalline polylactic acid resin. Furthermore, as the crystalline polylactic acid resin, poly L-lactic acid having an optical purity of at least 95% is used, and the segment (I) of the modifier for polylactic acid is composed of 98% by weight of a component derived from D-lactic acid. A configuration such as the above can be taken.

  As a method for producing the crystalline polylactic acid-based resin, various polymerization methods can be used, and a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, or the like can be employed.

  In the present invention, the addition amount of the polylactic acid modifier is preferably in the range of 1 to 50% by weight, more preferably 5 to 30% by weight based on the crystalline polylactic acid resin composition (modifier + polylactic acid resin). % Is preferred. When the addition amount of the modifier for polylactic acid is less than 1% by weight, the effect of improving heat resistance tends to be insufficient, and when it exceeds 50% by weight, the cost advantage tends to be reduced.

  The method for adding the modifier for polylactic acid is not particularly limited. For example, a predetermined amount of the modifier and crystalline polylactic acid resin are blended and supplied to an extruder, and a molded product is melt-extruded or a modifier. Alternatively, the crystalline polylactic acid resin may be melt-kneaded into chips in advance and melt-molded using this. As the extruder, a twin-screw extruder is preferable because of its high kneading effect, but a single-screw extruder may of course be used.

  The crystalline polylactic acid resin composition of the present invention can be used for fibers, films, injection molded articles and the like, but can be preferably used as a polylactic acid resin film having particularly high heat resistance.

  In the film containing the crystalline polylactic acid resin composition of the present invention, various particles can be added depending on the purpose and application. The particles to be added are not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include inorganic particles, organic particles, crosslinked polymer particles, and internal particles generated in the polymerization system. Two or more kinds of these particles may be added. From the viewpoint of the mechanical properties of the polylactic acid film, the amount of such particles added is preferably 0.01 to 10% by weight, more preferably 0.02 to 1% by weight.

Moreover, the average particle diameter of the particle to add becomes like this. Preferably it is 0.001-10 micrometers, More preferably, it is 0.01-2 micrometers. When the average particle diameter is within such a preferable range, defects of the film are hardly generated, and deterioration of transparency and moldability are not caused.
Furthermore, the film containing the crystalline polylactic acid resin composition of the present invention has additives as necessary, for example, flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, as long as the object and effects of the present invention are not impaired. An appropriate amount of an agent, an antistatic agent, a plasticizer, a tackifier, an organic lubricant such as a fatty acid ester or a wax, an antifoaming agent such as polysiloxane, or a coloring agent such as a pigment or dye can be blended.

  The film containing the crystalline polylactic acid resin composition of the present invention is preferably a film stretched at least in a uniaxial direction. The stretching direction may be either the longitudinal direction or the width direction of the film. Preferably, it is a biaxially stretched film stretched in both the longitudinal direction and the width direction of the film. This is because when an unstretched film is used at a temperature higher than the glass transition temperature of polylactic acid, thermal deformation or thermal crystallization occurs, which is not preferable from the viewpoint of quality stability.

The plane orientation coefficient fn of the film stretched as described above is preferably 3 × 10 −3 or more from the viewpoint of mechanical properties and heat resistance.

Here, the plane orientation coefficient fn is a numerical value defined by the refractive index of the film measured with an Abbe refractometer or the like, the refractive index in the longitudinal direction of the film is n MD , the refractive index in the width direction is n TD , When the refractive index in the thickness direction and n ZD, represented by the relational expression fn = (n MD + n TD ) / 2-n ZD. When it is difficult to measure the refractive index because the film is opaque, it can be obtained by other methods, such as X-ray, infrared spectroscopy, and Raman spectroscopy. In particular, the ATR method of infrared spectroscopy can be preferably used because the state of orientation of the film surface can be easily measured. In these cases, a correlation between the degree of orientation of the plane and the degree of orientation by other methods is obtained in advance using a film whose refractive index can be measured, and it can be obtained by converting to the degree of orientation of the target film. it can.

  Next, the case where a biaxially stretched film is produced will be specifically described.

  A raw material in which a predetermined amount of a modifier for polylactic acid and a crystalline polylactic acid resin are blended or a crystalline polylactic acid resin composition in which a modifier for polylactic acid has already been melt-kneaded is supplied to the extruder as a raw material, and 190 to 220 ° C. And melt extrusion. Foreign material is removed from the molten resin with a metal nonwoven fabric filter or a metal powder sintered filter, and the molten resin is guided to a slit base and extruded onto a casting drum. The molten sheet is brought into close contact with the casting drum by an electrostatic application method, an air knife method, a touch roll or the like, and rapidly cooled and solidified. In this way, an unstretched sheet is obtained.

  Next, the unstretched sheet is sent to a stretching apparatus and stretched by a method such as simultaneous or sequential biaxial stretching. In the case of sequential biaxial stretching, the stretching order may be the order of the longitudinal direction and the width direction of the film, or vice versa. Furthermore, in the sequential biaxial stretching, the stretching in the longitudinal direction or the width direction can be performed twice or more. As another method for obtaining a biaxially stretched film, it is of course possible to employ an inflation method in which a polymer is extruded from a ring-shaped die and stretched by blowing air.

  There is no restriction | limiting in particular about the extending | stretching method, Methods, such as roll extending | stretching and a tenter extending | stretching, are employable. The film shape during stretching may be any shape such as a flat shape or a tube shape. The stretching ratio in the longitudinal direction and the width direction of the film can be arbitrarily set according to the intended heat resistance, mechanical properties, etc., but preferably 1.5 mm in each direction in order to improve thickness unevenness. It is -6.0 times, More preferably, it is 1.5-4.5 times. Either the stretching ratio in the longitudinal direction or the width direction may be increased or the stretching ratio may be the same. The stretching speed is desirably 1,000% / minute to 1,000,000% / minute, and it is particularly preferable to form a film at a stretching speed of 300,000% / minute or less. The stretching temperature can be any temperature as long as it is in the range from the glass transition temperature to the melting point of the crystalline polylactic acid resin composition, but is preferably 60 to 150 ° C.

  Further, after this, the film can be heat-treated as necessary, but this heat-treatment can be carried out by any conventionally known method such as in an oven or on a heated roll. The heat treatment temperature can be any temperature below the melting point of the crystalline polylactic acid resin composition, but is preferably 80 to 150 ° C, more preferably 100 to 150 ° C. Moreover, although heat processing time can be made arbitrary, 0.1 to 60 second is preferable, More preferably, it is 1 to 20 second. Such heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Furthermore, re-stretching may be performed once or more in each direction, and then heat treatment may be performed.

  The thickness of the stretched film of the present invention can be freely determined according to the application to be used. The thickness is usually in the range of 0.5 to 500 μm, preferably from 1 to 250 μm, more preferably from 5 to 180 μm from the viewpoint of film formation stability.

  The crystalline polylactic acid resin film of the present invention can be improved in adhesion and printability as necessary by performing surface treatment such as corona discharge treatment, plasma treatment, and flame treatment. Various coatings may be applied, and this may be performed during the film forming process, or may be performed on a film that has been stretched. The type, coating method, and thickness of the coating coating compound are not particularly limited as long as the effects of the present invention are not impaired. If necessary, it can be used after being subjected to molding such as embossing or printing.

  The film containing the crystalline polylactic acid resin composition of the present invention obtained as described above is used as various industrial materials and packaging materials that require transparency, heat resistance and mechanical properties by a single film or a composite film. It is possible. Specifically, it can be used as various containers and packaging materials for food, hygiene, household goods, agriculture and horticulture.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(1) Ratio of polylactic acid segment and aromatic segment in the modifier The modifier is dissolved in deuterated chloroform and measured using H-NMR (GSX-400 type) manufactured by JEOL Ltd. The peak attributed to the polylactic acid moiety and the peak attributed to the aromatic ring were measured and determined by the peak area.

(2) Number average molecular weight of modifier for polylactic acid Measurement was performed using a Warters 2690 manufactured by Japan Warters Co., Ltd., using polystyrene as a standard, a column temperature of 40 ° C., and a chloroform solvent.

(3) Measurement of the amount of carboxyl end groups of the modifier The modifier was dissolved in ortho-cresol / chloroform (weight ratio 7/3) at 90 to 100 ° C., and the potential difference was measured with an alkali.

(4) Measurement of degree of plane orientation Δn Using sodium D line (wavelength 589 nm) as a light source and using an Abbe refractometer, the refractive index in the longitudinal direction (n MD ), the refractive index in the width direction (n TD ), and the thickness The refractive index (n ZD ) in the direction was measured, and the plane orientation coefficient (fn) was calculated from the following formula. The measured value was rounded off to the fourth decimal place.
fn = (n MD + n TD ) / 2-n ZD
(5) Elastic modulus, breaking stress A film sample was cut out to a width of 10 mm and a length of 150 mm, and this sample was subjected to an orientec Co., Ltd. tensile tester according to JIS Z 1702 to an initial length of 50 mm and a tensile speed of 300 mm / Minutes, a tensile test was performed in a heating oven at 80 ° C., and the elastic modulus (MPa) and the stress at break (MPa) were measured.

(Example 1) Production of polylactic acid / ethylene naphthalate modifier 100 parts by weight of 2,6-dimethylnaphthalate, 51 parts by weight of ethylene glycol, and 0.06 parts by weight of magnesium acetate tetrahydrate in the reactor The transesterification was carried out while dissolving at 180 ° C. and distilling methanol. The temperature in the reactor was finally set to 235 ° C., and the reactant was discharged from the reactor when the transesterification reaction was completed. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Next, 50 parts by weight of L-lactide in a dry state was charged into the reactor in the same manner as 50 parts by weight of the reaction product in the dry state, and dissolved at 140 ° C. Polymerization was carried out by adding 0.1 part by weight of tin 2-ethylhexanoate to the dissolved mixture.

  After polymerization for about 1 hour, 500 parts by weight of chloroform was added to dissolve the reaction product, and the solution was taken out. 1,000 parts by weight of methanol was prepared with respect to 100 parts by weight of the solution, and a chloroform solution was dropped into the methanol to precipitate a polylactic acid / ethylene naphthalate modifier. The precipitate was dissolved again in chloroform and then precipitated again in methanol, and purification was repeated.

  Thus, a polylactic acid / ethylene naphthalate modifier was obtained. The characteristics are shown in Table 1.

(Example 2) Production of polylactic acid / cyclohexane dimethylene terephthalate modifier 71 parts by weight of dimethyl terephthalate, 105 parts by weight of 1,4 cyclohexane dimethanol, 0.04 parts by weight of tetrabutyl titanate were charged in a reactor, respectively. Transesterification was carried out while dissolving at 140 ° C. and distilling methanol. The temperature in the reactor was finally set to 235 ° C., and the reactant was discharged from the reactor when the transesterification reaction was completed. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Using the reaction product in the dry state, a polylactic acid / cyclohexanedimethylene terephthalate modifier was obtained in the same manner as in Example 1. The characteristics are shown in Table 1.

(Example 3) Production of polylactic acid / spiroglycol terephthalate modifier 45 parts by weight of dimethyl terephthalate, 140 parts by weight of spiroglycol and 0.04 parts by weight of tetrabutyl titanate were respectively charged in a reactor and dissolved at 140 ° C. Then, transesterification was performed while distilling methanol. The temperature in the reactor was finally set to 235 ° C., and the reactant was discharged from the reactor when the transesterification reaction was completed. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of methanol, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again added dropwise to methanol to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Using the reaction product in the dry state, a polylactic acid / spiroglycol terephthalate modifier was obtained in the same manner as in Example 1. The characteristics are shown in Table 1.

(Example 4) Production of polylactic acid / bisphenoxyethanol fluorene terephthalate modifier 34 parts by weight of dimethyl terephthalate, 154 parts by weight of bisphenoxyethanol fluorene and 0.04 parts by weight of tetrabutyl titanate were charged in a reactor at 140 ° C. Transesterification was carried out while dissolving and distilling methanol. The temperature in the reactor was finally set to 235 ° C., and the reactant was discharged from the reactor when the transesterification reaction was completed. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Using the reaction product in the dry state, a polylactic acid / bisphenoxyethanol fluorene terephthalate modifier was obtained in the same manner as in Example 1. The characteristics are shown in Table 1.

(Example 5) Production of polylactic acid / isosorbate terephthalate modifier 70 parts by weight of dimethyl terephthalate, 105 parts by weight of isosorbate and 0.04 parts by weight of tetrabutyl titanate were charged in a reactor and dissolved at 140 ° C. Then, transesterification was performed while distilling methanol. The temperature in the reactor was finally set to 235 ° C., and the reactant was discharged from the reactor when the transesterification reaction was completed. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Using the reaction product in the dry state, a polylactic acid / isosorbate terephthalate modifier was obtained in the same manner as in Example 1. The characteristics are shown in Table 1.

(Example 6) Production of polylactic acid / ethylene phenylindane dicarboxylate modifier 93 parts by weight of 1,1,3-trimethyl-3-phenylindane-4 ', 5-dicarboxylic acid and 35 parts by weight of ethylene glycol Then, 0.04 part by weight of tetrabutyl titanate was charged into each reactor, and esterification was carried out while distilling water. The temperature in the reaction apparatus was finally set to 235 ° C., and when the esterification was completed, the reactant was discharged from the reaction apparatus. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  A polylactic acid / ethylenephenylindanedicarboxylate modifier was obtained in the same manner as in Example 1 using the reaction product in the dry state. The characteristics are shown in Table 1.

(Example 7) Production of polylactic acid / ethylene diphenylsulfone dicarboxylate modifier 92 parts by weight of 4,4'-diphenylsulfone dicarboxylic acid, 37 parts by weight of ethylene glycol, and 0.04 parts by weight of tetrabutyl titanate, respectively The reactor was charged and esterification was carried out while distilling water. The temperature in the reaction apparatus was finally set to 235 ° C., and when the esterification was completed, the reactant was discharged from the reaction apparatus. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1,000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  A polylactic acid / ethylene diphenylsulfone dicarboxylate modifier was obtained in the same manner as in Example 1 using the reaction product in the dry state. The characteristics are shown in Table 1.

(Example 8) Production of polylactic acid / ethylene biphenyl dicarboxylate modifier 90 parts by weight of 4,4'-diphenyldicarboxylic acid, 46 parts by weight of ethylene glycol, and 0.04 parts by weight of tetrabutyl titanate The esterification was carried out while distilling water. The temperature in the reaction apparatus was finally set to 235 ° C., and when the esterification was completed, the reactant was discharged from the reaction apparatus. The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Using the reaction product in the dry state, a polylactic acid / ethylene biphenyl dicarboxylate modifier was obtained in the same manner as in Example 1. The characteristics are shown in Table 1.

(Example 9) Production of polylactic acid / ethylene naphthalate modifier A polyethylene naphthalate chip having a number average molecular weight of 18,000 was melted at 290, and ethylene glycol was added thereto for depolymerization to obtain a number average molecular weight. Was 1,200.

  The reaction product was cooled and pulverized, and dissolved in 100 parts by weight of hexafluoroisopropanol (HFIP) with respect to 10 parts by weight of the reaction product. The solution was slowly dropped into 1000 parts by weight of water, and the precipitate was collected by centrifugation. The collected precipitate was dissolved again in HFIP and again dropped into water to repeat purification. The obtained precipitate was dried under reduced pressure at room temperature to obtain a dry state.

  Using the reaction product in the dry state, a polylactic acid / ethylene naphthalate modifier was obtained in the same manner as in Example 1. The characteristics are shown in Table 1.

(Examples 10 to 12, Comparative Examples 1 and 2)
Using the ethylene naphthalate obtained in Example 1, the blend ratio with L-lactide and the reaction time were changed to obtain various polylactic acid / ethylene naphthalate modifiers. The characteristics are shown in Table 1.

(Examples 13 to 24)
L polylactic acid resin having a D-form content of 1.2% is dried under reduced pressure at 120 ° C. for 5 hours, and various polylactic acid modifiers are dried under reduced pressure at 60 ° C. for 5 hours. The parts by weight and the modifier were blended at a ratio of 15 parts by weight and supplied to the extruder. The supplied raw material was melted at 210 ° C., filtered through a metal nonwoven fabric filter, and extruded from a slit-shaped die into a sheet shape.
The molten sheet was cast by applying static electricity on a drum cooled to 25 ° C. and rapidly solidified to produce an unstretched film. The film was stretched 3 times between the heating roll of 78 ° C. and the cooling roll of 25 ° C. at a speed of 15,000% / min in the longitudinal direction, and then the uniaxially stretched film was held with a clip and guided into the tenter, 80 While being heated at a temperature of ℃, the film was stretched 3.5 times at a rate of 20,000% / min in the transverse direction, and subjected to a heat treatment at 140 ° C. for 10 seconds while being fixed in the width direction. An axially stretched film was produced. The characteristic values of the obtained film are shown in Table 2.

(Example 25)
A film was obtained in the same manner as in Example 13 except that 99 parts by weight of the polylactic acid resin and 1 part by weight of the polylactic acid modifier of Example 1 were blended. The results are shown in Table 2.

(Comparative Example 3)
A film was obtained in the same manner as in Example 13 except that the modifier for polylactic acid was not added. The results are shown in Table 2.

(Comparative Examples 4 and 5)
Using the polylactic acid modifier obtained in Comparative Examples 1 and 2, films were obtained in the same manner as in Example 13. The results are shown in Table 2.

Claims (12)

  1. A segment (I) composed of a polylactic acid component having crystallinity and a segment (II) composed of an aromatic polyester component, and the weight ratio (I) / (II) of the segments (I) and (II) is 5 / Polylactic acid component segment containing polyester which is 95-70 / 30.
  2. The polylactic acid component segment-containing polyester according to claim 1, having a number average molecular weight of 28,000 or less.
  3. Segment (II) comprising an aromatic polyester component is a divalent naphthalene residue, a phenylene residue, a divalent cyclohexane residue, a spiroglycol residue, a fluorene residue, an isosorbate residue, a phenylindane residue, a diphenylsulfone The polylactic acid component segment containing polyester of Claim 1 or 2 containing the at least 1 sort (s) of component chosen from the group which consists of a residue, a biphenyl residue, and an imide residue.
  4. The ABA type or AB type block copolymer in which the A component is a segment (I) composed of a polylactic acid component and the B component is a segment (II) composed of an aromatic polyester component A polylactic acid component segment-containing polyester according to claim 1.
  5. The polylactic acid component segment containing polyester in any one of Claims 1-4 whose carboxyl group terminal content is 50 (equivalent / t) or less.
  6. The polylactic acid component segment containing polyester in any one of Claims 1-5 used as a modifier for polylactic acid.
  7. Step A for obtaining an aromatic polyester by esterification or transesterification from dicarboxylic acid and / or its ester-forming derivative and diol and / or its ester-forming derivative, and removing the free diol component from the obtained aromatic polyester The polylactic acid component segment-containing polyester according to any one of claims 1 to 6, which comprises a step B and a step C in which the aromatic polyester from which the free diol component has been removed and the lactide are dissolved and then subjected to ring-opening polymerization. Manufacturing method.
  8. A process D for depolymerizing an aromatic polyester with a diol to reduce the molecular weight, a process B for removing a free diol component from the obtained aromatic polyester, an aromatic polyester and a lactide from which the free diol component has been removed. The process for producing a polylactic acid component segment-containing polyester according to any one of claims 1 to 6, comprising a step C of ring-opening polymerization after each dissolution.
  9. The method for producing a polylactic acid component segment-containing polyester according to claim 8, wherein a molded product is used as the aromatic polyester.
  10. The crystalline polylactic acid resin composition containing the polylactic acid component segment containing polyester in any one of Claims 1-6.
  11. A film comprising the crystalline polylactic acid resin composition according to claim 10.
  12. The film according to claim 11, wherein the plane orientation coefficient fn is 3 × 10 −3 or more.
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KR100816417B1 (en) 2006-12-05 2008-03-25 에스케이씨 주식회사 Multilayered aliphatic polyester film
JP2010167766A (en) * 2008-12-27 2010-08-05 Tohcello Co Ltd Polylactic acid type gas barrier film and application thereof
JP5192815B2 (en) * 2005-10-03 2013-05-08 第一工業製薬株式会社 Functional filler and resin composition containing the same

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JP2010167766A (en) * 2008-12-27 2010-08-05 Tohcello Co Ltd Polylactic acid type gas barrier film and application thereof

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