JP4807544B2 - Polyester composition - Google Patents

Polyester composition Download PDF

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Publication number
JP4807544B2
JP4807544B2 JP2001231608A JP2001231608A JP4807544B2 JP 4807544 B2 JP4807544 B2 JP 4807544B2 JP 2001231608 A JP2001231608 A JP 2001231608A JP 2001231608 A JP2001231608 A JP 2001231608A JP 4807544 B2 JP4807544 B2 JP 4807544B2
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Japan
Prior art keywords
polyester
acid
polyhydroxycarboxylic acid
polyhydroxycarboxylic
aliphatic
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JP2003040990A5 (en
JP2003040990A (en
Inventor
崇 三原
正雄 上倉
彰志 今村
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Dic株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyhydroxycarboxylic acid copolymer The Polyhydroxycarboxylic Acid Impact resistance imparting agent that provides excellent impact resistance As Excellent impact resistance Polyester composition About.
[0002]
[Prior art]
At present, plastic products are used in various fields such as various food packaging materials, agricultural materials, medical instruments, adhesives, and miscellaneous goods. As typical general-purpose resins, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyamide, polyurethane and the like are known.
[0003]
However, as a final disposal method after use of these plastic products, in fact, incineration and landfilling are performed. In addition, such waste causes global environmental problems such as lack of landfills, landscape obstruction, and threats to marine life.
[0004]
Under such circumstances, there is a strong demand for a transition from a mass production / consumption / disposal type economic and social system of plastic to a recycling type economic and social system. In response to this, the market development of biodegradable plastics has been highlighted.
[0005]
Biodegradable polymers are roughly classified into the following three types. These are natural systems such as starch, microbial systems such as polyhydroxybutyrate, and chemical synthesis systems such as polylactic acid and polycaprolactone.
[0006]
Unlike general plastics, these biodegradable polymers easily decompose completely and eventually become water and carbon dioxide. In addition, since the burned calories are low, the furnace does not hurt even when incinerated, and no harmful gas is generated during combustion. Since it is possible to use easily recyclable plant resources as starting materials, it is possible to escape from exhausted petroleum resources. Because of these advantages, it is currently expected as an alternative to general-purpose resins.
[0007]
In particular, polyhydroxycarboxylic acids such as polylactic acid are synthesized from natural raw materials such as corn, and are known to be excellent in transparency, heat resistance, melt moldability, toughness, high rigidity, and the like. However, since it is very fragile, its application to molded articles and the like is limited. For this reason, research has been conducted to improve the brittleness, that is, to improve the flexibility and impact resistance, by adding a plasticizer to polylactic acid or by copolymerization to maintain the excellent properties of polylactic acid. It was.
[0008]
For example, as an example of adding a plasticizer to polylactic acid, the specification of US Pat. No. 1995970 discloses a method for enhancing softening and tear strength by adding dibutyl phthalate and nitrocellulose to polylactic acid. Yes. U.S. Pat. No. 3,498,957 discloses a melting plasticizer that reduces the viscosity during polymerization of polylactic acid by adding glycol diesters or dibasic acid diesters during polymerization.
[0009]
US Pat. No. 5,180,765 discloses a method for softening by adding a lactic acid oligomer or lactide to polylactic acid. However, this method is known to have problems such as a decrease in heat resistance and the tendency of hydrolysis of the polymer itself.
[0010]
European Patent No. 226061 discloses a polylactic acid composition containing a plasticizer such as triethyl citrate as an application to medical materials.
JP-A-2-117 discloses a polylactic acid composition containing acetates as a plasticizer, which is useful as a plasticizing technique for biomaterials for implantation in the body such as medical films and rods. It is disclosed.
[0011]
JP-A-4-335060 discloses a composition containing polylactic acid and a plasticizer, more specifically, phthalic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, hydroxy polyvalent carboxylic acid ester, fatty acid ester, A polylactic acid composition containing a general-purpose plasticizer for a general-purpose resin such as a monohydric alcohol ester, an epoxy-based plasticizer, a polyester-based plasticizer, or a mixture thereof is disclosed.
[0012]
Although these technologies allow softening of polylactic acid, the heat resistance of plasticized polylactic acid is greatly reduced, soft, but not accompanied by impact strength, cracking properties during bending, and polylactic acid during kneading. There are still many problems, such as accompanied by a decrease in the molecular weight of lactic acid. Moreover, these low molecular plasticizers cannot avoid the problem of vaporization of the plasticizer during processing and bleeding out.
[0013]
Polyester plasticizers were also difficult to obtain sufficient flexibility, and bleed out during storage was severe. As other polymer plasticizers, polyesters such as polycaprolactone and polyethers have been reported. In JP-A-8-199052, polyethers are useful as plasticizers for polylactic acid. JP-A-8-283557 discloses that an aliphatic polyester composed of an aliphatic dicarboxylic acid and an aliphatic diol is useful as a plasticizer for softening a polymer mainly composed of polylactic acid. It is disclosed that.
[0014]
However, in either case, only an amount that slightly improves the impact strength of polylactic acid can be added, and attempts to achieve significant softening result in a decrease in heat-resistant temperature and bleed-out as in the case of a low molecular weight plasticizer, Further, the transparency is also lowered depending on the kind and amount of the plasticizer. Further, although flexibility can be imparted, it has the disadvantages that it is weak against impact and has low crazing resistance.
[0015]
Further, JP-A-9-137047 discloses a polylactic acid composition obtained by copolymerizing lactide and a low melting point polyester, and further adding a copolymer or homopolymer having a similar structure as the third component. .
[0016]
However, aliphatic polyesters having high crystallinity and high glass transition temperature even when the melting point of the low-melting polyester described is 130 ° C. or lower have a low degree of improvement in impact strength even when the third component is added. This suggests that the impact strength of the polyhydroxycarboxylic acid and other polyhydroxycarboxylic acids cannot be improved only by the impact strength of the additive and the structural similarity only with the base polymer.
[0017]
On the other hand, in the copolymerization method, JP-A-7-173266 discloses lactide and ring-opening polymerization polymerization of aromatic dicarboxylic acid and / or aromatic dicarboxylic acid and aliphatic diol. A method for producing a lactic acid copolymer polyester obtained by reacting in the presence of a catalyst is disclosed. There is a description that the sheet of lactic acid copolymer polyester obtained by this production method exhibits excellent flexibility and transparency. However, a method for producing a lactic acid copolymer polyester using polylactic acid which is commercially available and easily available has not been known so far.
[0018]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to use polyhydroxycarboxylic acid and polyester, impart excellent impact resistance and flexibility to polyhydroxycarboxylic acid, maintain heat resistance, and suppress bleeding out. Possible impact resistance agent Polyester composition containing Is to provide.
[0020]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the inventors of the present invention melted polyhydroxycarboxylic acid and polyester in the presence of a transesterification catalyst and reacted under reduced pressure to achieve a sufficient high molecular weight and application. It has been found that a copolymer having high impact resistance, flexibility and biodegradability can be obtained, and the present invention has been solved. In addition, the copolymer can improve the flexibility and impact resistance superior to polyhydroxycarboxylic acids, maintain heat resistance, and suppress bleed out. In the case of lactic acid, it discovered that it could be used as a modifier which can maintain transparency, and came to solve this invention.
[0021]
That is, the present invention provides a polyhydroxycarboxylic acid (A) having a weight average molecular weight of 5,000 to 400,000 and a polyester (B) comprising a dicarboxylic acid having a weight average molecular weight of 5,000 to 200,000 and a diol. Melt, then add transesterification catalyst (C) and transesterify under reduced pressure Obtained by Polyhydroxycarboxylic acid copolymer It contains an impact resistance imparting agent and polyhydroxycarboxylic acid. A polyester composition is provided.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
A polyhydroxycarboxylic acid (A) having a weight average molecular weight of 5,000 to 400,000 and a polyester (B) comprising a dicarboxylic acid having a weight average molecular weight of 5,000 to 400,000 and a diol are melted and then transesterified. About the manufacturing method of the copolymer (henceforth a polyhydroxycarboxylic acid type copolymer) of polyhydroxycarboxylic acid and polyester characterized by adding a catalyst (C) and carrying out transesterification under reduced pressure below. Explained.
[0023]
First, the present invention Used in A method for producing the polyhydroxycarboxylic acid copolymer will be described. The A manufacturing method supplies the raw material polyhydroxycarboxylic acid (A), polyester (B) which consists of diol and dicarboxylic acid to a reactor, and is made to melt | dissolve in an inert gas atmosphere at 100-280 degreeC.
[0024]
Here, the reactor is not particularly limited, but examples of the batch reactor include a vertical or horizontal tank reactor or a kneader with a stirring blade. As the continuous reactor, a twin-screw kneading extruder is preferably exemplified. A twin-screw kneading extruder has a shaft that rotates in the same direction or a different direction, and a screw that meshes with each other. The cylinder (cylindrical part) supplies and devolatilizes raw materials and additives, and an inert gas. A vent hole for carrying out the supply, reaction under reduced pressure, and venting thereof, that is, having a large opening area and a large number of holes, specifically one to five, etc. be able to. In these attached twin-screw kneading extruders, the raw material or the polymer during and after polymerization can be stirred, melted and mixed very effectively, and the reaction can proceed rapidly. In addition to this, a single-screw kneading extruder can be used, but a twin-screw kneading extruder is preferably used from the viewpoint of kneading efficiency.
[0025]
The transesterification catalyst (C) is added to the mixture of the molten polyhydroxycarboxylic acid (A) and the polyester (B), the reaction temperature is 100 to 280 ° C., the degree of vacuum is 5,000 pascals (hereinafter abbreviated as Pa). The transesterification reaction is carried out below.
[0026]
Here, the polyhydroxycarboxylic acid (A) used in the present invention is composed of a repeating unit of an aliphatic carboxylic acid having a hydroxyl group in the molecule, and examples thereof include polylactic acid, polycaprolactone, polyglycolic acid, polyhydroxylic acid. Examples include butyrate, polyhydroxyvalerate, polylactic acid / glycolic acid copolymer, polyhydroxybutyrate / valerate copolymer, and the like. Moreover, when it has asymmetric carbon in a repeating unit like polylactic acid, any of a L body, D body, a mixture of L body and D body, ie, a racemic body, may be sufficient.
[0027]
The polyhydroxycarboxylic acid (A) may be obtained by dehydration polycondensation of hydroxycarboxylic acid, or may be obtained by ring-opening polymerization of lactones such as lactide and glycolide.
[0028]
The polyhydroxycarboxylic acid (A) used in the present invention preferably has a weight average molecular weight in the range of 5,000 to 400,000, more preferably 10,000 to 250,000.
[0029]
On the other hand, the polyester (B) used in the present invention has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 200,000, and more preferably 20,000 to 15. 0 Aromatic and / or aliphatic polyesters composed of 20,000, particularly preferably 20,000 to 100,000 aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids and aliphatic diols are used.
[0030]
As the polyester (B) used in the present invention, for example, a polyester obtained by a known and common polycondensation reaction from a combination of a diol and a dicarboxylic acid shown below can be used.
[0031]
The diol used in the present invention is not particularly limited as long as it is an aliphatic diol having a chain hydrocarbon or an alicyclic hydrocarbon. Among them, an aliphatic diol having 2 to 45 carbon atoms is preferably exemplified. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, propylene glycol, 1,3-butanediol, 1,2-butanediol, neopentyl Glycol, 3,3-diethyl-1,3-propanediol,
[0032]
3,3-dibutyl-1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2- Methyl-2,4-pentanediol, 1,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, n-butoxyethylene glycol, Examples include cyclohexanedimethanol, hydrogenated bisphenol A, dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, xylylene glycol, and phenylethylene glycol. Two or more of these diols can be used in combination.
[0033]
On the other hand, the dicarboxylic acid used in the present invention is not particularly limited as long as it is a chain hydrocarbon, an aliphatic dicarboxylic acid having an alicyclic hydrocarbon, or an aromatic dicarboxylic acid having an aromatic ring. Preferred examples include aliphatic dicarboxylic acids having 4 to 45 carbon atoms or aromatic dicarboxylic acids having 4 to 45 carbon atoms. Examples of aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid. Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid and dimer acid; and unsaturated aliphatic dicarboxylic acids such as fumaric acid. Aromatic dicarboxylic acids include phthalic acid, terephthalic acid Acid, isophthalic acid, naphthalenedicarboxylic acid and the like can be mentioned. Two or more of these dicarboxylic acids can be used in combination.
[0034]
The melting point of the polyester (B) composed of diol and dicarboxylic acid is preferably 150 ° C. or less. Examples of the melting point of polyester (B) include, but are not limited to, polyethylene succinate at about 102 ° C, polypropylene succinate at about -2 ° C, polybutylene succinate at about 113 ° C, and polyethylene adipate at about 44 ° C, polypropylene adipate about 58 ° C, polybutylene adipate about 58 ° C, polyethylene sebacate about 63 ° C, polypropylene sebacate about -41 ° C, polybutylene adipate / terephthalate (feeding molar ratio; adipic acid: terephthalic acid = 1: 1) is about 120 ° C, and these can be preferably used as the polyester (B).
[0035]
Polyester (B) can be obtained by a known and commonly used production method. For example, diol and dicarboxylic acid are gradually heated at a rate of 5 to 10 ° C. per hour at a reaction temperature in the range of 130 to 240 ° C. in a nitrogen atmosphere at a molar ratio of 1: 1.5 to 1: 1. While stirring, water is distilled off. After the reaction for 4 to 12 hours, excess diol is distilled off while gradually increasing the degree of vacuum in the range of 0.1 KPa to 100 KPa. After reducing the pressure for 2 to 3 hours, the transesterification catalyst (C) and the antioxidant are added, and the mixture is reacted at 200 to 240 ° C. for 4 to 12 hours while reducing the pressure at 0.5 KPa or less. Can be obtained.
[0036]
As the transesterification catalyst used at this time, a catalyst comprising at least one metal or metal compound selected from the group consisting of groups II, III and IV of the periodic table can be used. More specifically, a catalyst comprising a metal or a metal compound such as Ti, Sn, Zn, Mg, Al, Zr, and Hf is preferable. Titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, tin octoate More preferred are tin 2-ethylhexanoate, zinc acetylacetonate, zinc acetate, magnesium acetate, zirconium tetrachloride, hafnium tetrachloride, hafnium tetrachloride, and a hafnium tetrachloride complex.
[0037]
Moreover, the usage-amount of the transesterification catalyst in the case of manufacturing polyester (B) is 10-1000 ppm with respect to polyester (B), Preferably it is 20-500 ppm, More preferably, it is 30-300 ppm.
[0038]
In order to reduce the coloration of the polyester, which is a problem during the transesterification reaction, it is preferable to further add 10 to 2000 ppm of an antioxidant such as a phosphite compound.
[0039]
In order to further reduce the melt viscosity, the polyester (B) obtained by the above-described production method is branched, or the polyester is further reacted with a known and conventional acid anhydride or polyisocyanate by a known and conventional method. To increase the molecular weight.
[0040]
Next, the melting temperature is not particularly limited as long as it is equal to or lower than the thermal decomposition temperature of the polyhydroxycarboxylic acid (A) in order to melt the polyhydroxycarboxylic acid (A) and the polyester (B), but the polyhydroxycarboxylic acid (A ) Melting point (hereinafter may be abbreviated as Tm) + 60 ° C. or lower, more preferably Tm + 50 ° C. or lower of polyhydroxycarboxylic acid (A). Examples of the melting points of the polyhydroxycarboxylic acid (A) and the polyester (B) are shown below.
[0041]
Examples of the melting point of the polyhydroxycarboxylic acid (A) include polylactic acid of about 160 to 175 ° C, polycaprolactone of about 60 ° C, polyglycolic acid of about 235 ° C, and polyhydroxybutyrate / valerate copolymer of about 120. Up to 165 ° C. Accordingly, the melting temperature is preferably in the range of 100 to 280 ° C.
[0042]
The mass ratio between the polyhydroxycarboxylic acid (A) and the polyester (B) is not particularly limited, but 99: 1 to 15:85 is preferable, and 95: 5 to 20:80 is particularly preferable. In particular, when used as an impact-imparting agent for polyhydroxycarboxylic acid, which will be described later, in order to increase the compatibility with polyhydroxycarboxylic acid, the mass ratio of polyhydroxycarboxylic acid (A) to polyester (B) is 99: 1 to 40:60.
[0043]
Next, as the transesterification catalyst (C) used in the present invention, a catalyst comprising at least one metal or metal compound selected from the group consisting of groups II, III, and IV of the periodic table can be used. Preferably, it is a metal or a metal compound such as Ti, Sn, Zn, Mg, Al, Zr, Hf, more preferably a titanium-based alkoxide catalyst, specifically Ti (OC n H 2n + 1 ) 4 (Wherein n is an integer value of 1 to 8), and titanium tetraisopropoxide or titanium tetrabutoxide is preferable.
[0044]
The amount of the transesterification catalyst (C) used in the present invention is not particularly limited as long as it substantially accelerates the reaction rate. However, if the amount used is large, depending on the reaction temperature, reaction time, and degree of vacuum, the resin is colored, and when polylactic acid is used as the polyhydroxycarboxylic acid (A), especially polyhydroxycarboxylic acid (A), transesterification Depolymerization is promoted by the action of the catalyst (C). Therefore, although the usage-amount of a catalyst changes with reaction conditions, it is 10-1000 ppm with respect to the whole quantity of hydroxycarboxylic acid (A) and polyester (B), Preferably it is 20-800 ppm, More preferably, it is 30-500 ppm. It is a range. The amount used is preferable because the coloration and depolymerization of the resulting copolymer can be minimized.
[0045]
The reaction temperature is not particularly limited as long as it is higher than the melting temperature of the raw material polyhydroxycarboxylic acid (A) and polyester (B) and lower than the thermal decomposition temperature of polyhydroxycarboxylic acid (A) or polyester (B). 100 to 280 ° C is preferable, and a range of 180 to 250 ° C is more preferable.
[0046]
The degree of vacuum is not particularly limited as long as it substantially accelerates the reaction rate, but is preferably 5,000 Pa or less, more preferably 2,000 Pa or less, and particularly preferably 700 Pa or less.
[0047]
the above The polyhydroxycarboxylic acid-based copolymer obtained by the production method of (1) can be used to remove monomers remaining in the copolymer and the transesterification catalyst (C) or to transesterify the catalyst (C) by a conventionally known method. By deactivating, storage stability can be further improved.
[0048]
As a method for removing the remaining monomer, it may be removed by vacuum devolatilization after the catalyst deactivation treatment. As a method for removing the transesterification catalyst (C), for example, a methanol / hydrochloric acid aqueous solution, or an acetone / hydrochloric acid aqueous solution as a solvent, or a mixed solution thereof, a resin pellet of a polyhydroxycarboxylic acid copolymer is attached, Examples include a method in which a polyhydroxycarboxylic acid copolymer is mixed with the above solution in a solution state and washed while the polymer is precipitated. By such a method, a trace amount of residual monomer, oligomer, etc. can be simultaneously removed by washing. Moreover, as a deactivation method of a transesterification catalyst (C), a catalyst deactivator can be added and the transesterification catalyst (C) can be deactivated after manufacture or manufacture of a polyhydroxycarboxylic acid type copolymer. Usually, the catalyst deactivator is coordinated to the transesterification catalyst (C) in the polyhydroxycarboxylic acid copolymer in a chelate-like form and contained in the polyhydroxycarboxylic acid copolymer. It may be removed by such as.
[0049]
The addition amount of the catalyst deactivator varies depending on the type and reaction conditions of the transesterification catalyst (C) used in the production of the polyhydroxycarboxylic acid copolymer, but deactivates the transesterification catalyst (C) used. The amount is not particularly limited, but it is preferably used in an amount of 0.001 to 10 parts per 1 part of the transesterification catalyst (C) in terms of mass before taking out the polymer after completion of the reaction or during kneading. It is more preferable to use 0.1 to 5 parts, and it is more preferable to use 0.5 to 3 parts.
[0050]
The catalyst deactivator used in the present invention may be a conventionally known catalyst deactivator, and examples thereof include chelating agents and acidic phosphate esters.
[0051]
the above The polyhydroxycarboxylic acid copolymer obtained by the production method is more preferably in the range of 10,000 to 400,000, still more preferably in the range of 10,000 to 300,000. A range of 000 to 250,000 is particularly preferable.
[0052]
Also, the above The form of the copolymer of the polyhydroxycarboxylic acid-based copolymer obtained by the production method is such that when the polyhydroxycarboxylic acid (A) is denoted by A and the polyester (B) is denoted by B, an AB type block copolymer is obtained. It may be a polymer, an ABA type block copolymer, or any other type.
[0053]
Also, the above The polyhydroxycarboxylic acid-based copolymer obtained by the production method of the above has excellent flexibility, transparency, impact resistance and decomposition, depending on the mass ratio of the polyhydroxycarboxylic acid (A) and the polyester (B). Exhibits sex.
[0054]
For example, when the mass ratio of the polyhydroxycarboxylic acid (A) and the polyester (B) is (A) :( B) = 25: 75 to 98: 2, Said The polyhydroxycarboxylic acid copolymer exhibits excellent flexibility. For example, the storage elastic modulus (E ′) at room temperature measured by RSAII manufactured by Rheometrics Co., Ltd. is in the range of 0.5 KPa to 3.0 KPa, and more excellent is 0.00. The range of 6 KPa-2.5 KPa is shown.
[0055]
Moreover, Tg of all the compositions shows 45 degreeC or more. It is superior to low molecular plasticizers and general polyester plasticizers from the viewpoint of not reducing heat resistance. In addition, the polyhydroxycarboxylic acid copolymer can maintain excellent transparency. For example, when polylactic acid is used as the polyhydroxycarboxylic acid (A), the haze value of a 200 μm thick press film when the mass ratio of polylactic acid to polyester (B) is 90:10 is 35% or less, More preferably, it is 1-30%, More preferably, it is 1-25%. The polyhydroxycarboxylic acid-based copolymer has a DuPont impact strength of 0.15 J or more, preferably 0.2 to 5 J, in an unstretched film or a stretched film, or 1 J or more in a stretched heat set film, preferably It has a film impact of 1-10J.
[0056]
When a molded product using the polyhydroxycarboxylic acid copolymer or a 10 × 10 cm square, 250 μm thick film is left in a constant temperature and humidity chamber at 35 ° C. and 80% humidity, bleeding from the surface of the molded product for 60 days or more. Things do not appear.
[0057]
further The above manufacturing method The polyhydroxycarboxylic acid copolymer obtained in (1) has good decomposability and is subject to degradation due to hydrolysis, biodegradation and the like even when dumped in the sea. In seawater, the strength of the resin deteriorates within a few months, and it can be decomposed without maintaining its outer shape. In addition, when compost is used, it is biodegraded before it remains in its original form in a shorter period of time, and no toxic gases or toxic substances are emitted even when incinerated.
[0058]
Also, the above The polyhydroxycarboxylic acid-based copolymer can be preferably used as an impact resistance imparting agent for the polyhydroxycarboxylic acid. However, in the present invention, the “impact resistance imparting agent” means an additive capable of imparting impact resistance by being added to the resin.
[0059]
Among the polyhydroxycarboxylic acid copolymers (D) obtained by the production method described above, a polyhydroxycarboxylic acid copolymer having a weight average molecular weight of 10,000 or more and a glass transition temperature of 60 ° C. or less ( What consists of D ') is preferably used as an impact resistance imparting agent of the present invention. By adding an impact resistance-imparting agent to the polyhydroxycarboxylic acid (E), which is a matrix polymer, the impact resistance, flexibility, and tensile elongation of the matrix polymer are improved, heat resistance is maintained, and bleeding out is suppressed. be able to.
[0060]
However, although the polyhydroxycarboxylic acid copolymer (D ′) preferably has a weight average molecular weight of 10,000 or more, it further maintains transparency, improves suppression of bleed-out, and has excellent resistance to resistance. In order to impart impact properties, the weight average molecular weight is preferably in the range of 20,000 to 200,000, more preferably in the range of 30,000 to 200,000, and 40,000 to 150,000. The range is particularly preferable.
[0061]
By adding a lactic acid-based polyester having a weight average molecular weight of 10,000 or more, a sufficient plastic effect and impact strength can be imparted when added to polyhydroxycarboxylic acid, and the transparency of the composition is lowered. I will not let you. On the other hand, although there is no upper limit on the molecular weight, it is generally 200,000 or less, and is 150,000 or less for ease of use.
[0062]
The glass transition temperature (Tg) of the polyhydroxycarboxylic acid copolymer (D ′) is preferably in the range of −70 ° C. to 60 ° C., particularly preferably in the range of −65 ° C. to 60 ° C.
[0063]
The polyhydroxycarboxylic acid copolymer (D ′), which is an impact resistance imparting agent of the present invention designed so that the weight average molecular weight is 10,000 or more and the glass transition temperature is 60 ° C. or less, is 20 The storage elastic modulus (E ′) at ° C. is 2.5 gigapascal (GPa) or less, preferably 0.1 to 2.0 GPa.
[0064]
next, the above The polyester composition (F) containing the impact resistance imparting agent and polyhydroxycarboxylic acid (E) will be described.
[0065]
Examples of the polyhydroxycarboxylic acid (E) that is a matrix polymer used in the polyester composition (F) of the present invention include polylactic acid, polyglycolic acid, polyhydroxybutyrate, polyhydroxyvalerate, hydroxybutyrate and hydroxyvalerate. And a copolymer of polycaprolactone. Among these, polylactic acid, polyhydroxybutyrate, and polycaprolactone are preferable, and polylactic acid is particularly preferable. The weight average molecular weight of these polyhydroxycarboxylic acids is not particularly limited, but in general, the weight average molecular weight is preferably 50,000 or more, more preferably 70,000 or more, particularly preferably 100,000 or more, And the thing of 500,000 or less is preferable.
[0066]
The present invention Used in The impact resistance imparting agent may be kneaded with polyhydroxycarboxylic acid (E) such as polylactic acid as it is, or may be used in the state of a masterbatch previously blended with polyhydroxycarboxylic acid (E) at a high concentration. .
[0067]
The present invention Used in The kneading ratio of the polyhydroxycarboxylic acid copolymer (D ′) and the polyhydroxycarboxylic acid (E) constituting the impact resistance-imparting agent is not particularly limited as long as the effect of the present invention is achieved. However, it is preferably (D ′) :( E) = 3: 97 to 70:30, more preferably 5:95 to 50:50, particularly preferably 5:95 to 40:60. Within this composition ratio range, the heat resistance, impact resistance and bleed-out property of the polyester composition are improved in a well-balanced manner.
[0068]
The kneading conditions of the impact resistance-imparting agent and the polyhydroxycarboxylic acid (E) are kneading above the melting point of the polyhydroxycarboxylic acid (E) to be added. Used in Since the melting point of the polyhydroxycarboxylic acid copolymer (D ′) constituting the impact resistance imparting agent (E) is 100 to 280 ° C., it is preferably around 180 to 200 ° C. When it greatly exceeds 200 ° C., it is necessary to adjust the kneading time, the kneading rotation speed, etc., taking into account the decrease in the molecular weight of the polyhydroxycarboxylic acid (E).
[0069]
As the kneading equipment, known and conventional equipment such as an extruder, a kneader, and a batch kneader are used. Further, kneading in a reaction kettle or blending using a static mixer is possible when the viscosity is high. Although similar blending is possible even with wet blending using a solvent, it is preferable to devolatilize the solvent at a high temperature in a short time to prevent separation of the polymer.
[0070]
The polyester composition (F) of the present invention can be easily processed into a film by a known and common method such as extrusion molding such as T-die casting or inflation molding. It is also possible to perform multilayering with a plurality of extruders. In addition, although the sheet | seat and the film are conventionally used properly by normal thickness, in order to avoid confusion in this invention, it shall generically call it a film. The thickness of the film of the present invention is not particularly limited, but generally refers to 5 μm to 2 mm.
[0071]
The polyester composition (F) is easily hydrolyzed due to its high hygroscopicity, and can be easily processed with a general single screw extruder when processing packaging materials such as films. When a twin-screw extruder equipped with is used, since the dehydration effect is high, pre-drying is not necessary and efficient film formation is possible.
[0072]
When using a single screw extruder, in order to avoid hydrolysis in the extruder, it is preferable to perform dehumidification drying with a vacuum dryer or the like, and to suppress the moisture in the raw material to 50 ppm or less. The appropriate extrusion temperature varies depending on the molecular weight and residual lactide amount of the polyester composition (F) to be used, but is preferably equal to or higher than the flow start temperature.
[0073]
Although the melting temperature at the time of film-forming a polyester composition (F) by T die-casting is not specifically limited, Usually, it is 10-60 degreeC temperature higher than melting | fusing point of a polyester composition (F). The melt-extruded film is usually cast so as to have a predetermined thickness, and cooled if necessary. At that time, when the film is thick, a touch roll, an air knife, and when it is thin, electrostatic pinning is properly used to form a uniform film.
[0074]
The film formed can be uniaxially and biaxially stretched at a temperature not lower than the glass transition point and not higher than the melting point by a known and common method such as a tenter method or an inflation method. By performing the stretching treatment, molecular orientation can be generated, and physical properties such as impact resistance, rigidity, and transparency can be improved.
[0075]
In the case of uniaxial stretching, it is preferable to stretch 1.3 to 10 times in the longitudinal direction or the transverse direction by longitudinal stretching by a roll method or transverse stretching by a tenter. In the case of biaxial stretching, longitudinal stretching by a roll method and transverse stretching by a tenter can be mentioned. As the method, the first-axis stretching and the second-axis stretching may be performed sequentially or simultaneously. The draw ratio is preferably 1.3 to 6 times in the longitudinal direction and the transverse direction. If the draw ratio is lower than this, it is difficult to obtain a film having a sufficiently satisfactory strength, and if it is high, the film will be broken during stretching. In addition, when shrinkage | contraction property of a shrink film etc. is requested | required especially at the time of heating, high magnification extending | stretching of 3-6 times etc. to a uniaxial or biaxial direction is preferable.
[0076]
The stretching temperature is preferably in the range of the glass transition point (hereinafter referred to as Tg) to (Tg + 50) ° C. of the polyhydroxycarboxylic acid copolymer (D ′), particularly preferably in the range of Tg to (Tg + 30) ° C. If the stretching temperature is less than Tg, stretching is difficult, and if it exceeds (Tg + 50) ° C., strength improvement due to stretching may not be observed.
[0077]
In addition, in order to improve heat resistance, heat setting can be performed immediately after stretching to improve the heat resistance characteristics by promoting strain removal or crystallization.
[0078]
Further, when heat setting treatment is performed under tension immediately after stretching in order to improve heat resistance, heat resistance can be improved by promoting the removal of strain or crystallization. The heat setting treatment temperature can be performed at a temperature 20 ° C. lower than the crystallization temperature (Tc) to a temperature lower than the melting point of the lactic acid polymer, but is preferably in the range of 70 to 150 ° C., more preferably in the range of 90 to 150 ° C. This is desirable because it improves not only the heat resistance but also other film properties such as tensile elongation.
[0079]
The heat setting time is usually from 1 second to 30 minutes, but considering practicality such as productivity, the shorter the time, the better. Therefore, it is preferably 1 second to 3 minutes, more preferably 1 second to 1 minute. It is.
[0080]
When forming these films, a general filler, for example, an inorganic filler such as talc, calcium carbonate, silica, clay, diatomaceous earth, pearlite, or an organic filler such as wood powder may be mixed and added. .
[0081]
Moreover, a well-known and usual antioxidant, a ultraviolet absorber, a stabilizer, a lubricant, surfactant, a coloring agent, and a foaming agent can also be used for the polyester composition (F) of this invention. These addition amounts are not particularly limited as long as the effects of the present invention are not impaired, but are added in an amount of 0.01 to 10% in terms of mass with respect to the polyester composition (F). It is preferable to do.
[0082]
The polyester composition of the present invention can be impregnated in advance, or can be made into a foam by directly supplying it into the extruder during the extrusion process. Also, lamination with paper, aluminum foil or other degradable polymer film is possible by extrusion lamination, dry lamination or coextrusion.
[0083]
As a secondary processing method of the film, a known and commonly used method such as a vacuum forming method, a pressure forming method, or a vacuum / pressure forming method can be used. The polyester composition (F) of the present invention can be formed into a film using an existing apparatus used for film production of general-purpose resins.
[0084]
In the case of vacuum forming or vacuum / pressure forming, plug assist molding may be performed. The stretched film is preferably subjected to pressure forming. In addition, the heating and cooling of the mold can be arbitrarily used at the time of molding. In particular, the heat resistance can be improved by heating the mold above the crystallization temperature and actively proceeding with crystallization.
[0085]
Inflation molding can be easily performed with a molding device equipped with a normal circular die and air ring, and no special accessory device is required. At this time, in order to avoid uneven thickness, the die, air ring or winder may be rotated.
[0086]
For film production, a bag-like product can be obtained by easily heat-sealing with a normal bag making machine such as a horizontal pillow bag making machine, a vertical pillow bag making machine, or a twist back bag making machine.
[0087]
When a processed product other than these films is obtained, a mold such as a container can be obtained without problems using a normal injection molding machine.
[0088]
Blow molding is also easy, and single layer and multilayer bottles can be easily molded by using an existing molding machine. There is no particular problem with press molding, and a single layer or a laminated product can be obtained with an ordinary molding machine.
[0089]
The polyester composition (F) of the present invention exhibits excellent impact resistance by adding an impact resistance imparting agent. Also, By adjusting the addition amount of the impact resistance imparting agent, the non-stretched film or stretched film has a DuPont impact strength of 0.20 J or more, preferably 0.3 to 5 J, or the stretched heat set film has 1 J or more. , Preferably having a film impact of 1-10 J.
[0090]
Furthermore, the polyester composition (F) of the present invention is , By adding an impact resistance-imparting agent, excellent flexibility is exhibited. For example, the composition (F) is formed into a film, and the storage elastic modulus at room temperature (E ′) measured by RSAII manufactured by Rheometrics Co., Ltd. Shows the range of 0.5-3.0 KPa, and the more excellent thing shows the range of 0.6-2.4 KPa.
[0091]
In addition, each composition is superior to low molecular plasticizers and general polyester plasticizers in that Tg is maintained at 50 ° C. or higher and the heat resistance of the base polymer is not lowered while improving the impact resistance.
[0092]
Also, the above The impact resistance-imparting agent can maintain excellent transparency even when added to the polyhydroxycarboxylic acid (E). For example, the haze value of a press film having a thickness of 250 μm in which 30 parts of an impact resistance imparting agent is added to 100 parts of polylactic acid in terms of mass is 35% or less, more preferably 1 to 30%, and still more preferably 1 to 25%. It is.
[0093]
the above When a molded product or a film (10 × 10 cm square, 250 μm thick) using the polyester composition (F) containing the impact resistance imparting agent is left in a constant temperature and humidity chamber at 35 ° C. and 80% humidity, Bleed material does not appear from the surface of the molded product for more than 60 days.
[0094]
further, the above Improves impact resistance Agent and The polyester composition (F) containing the polyhydroxycarboxylic acid (E) has good degradability and is subject to degradation due to hydrolysis, biodegradation, etc. even when it is dumped in the sea. In seawater, the strength of the resin deteriorates within a few months, and it can be decomposed without maintaining its outer shape. In addition, when compost is used, it is biodegraded before it remains in its original form in a shorter period of time, and no toxic gases or toxic substances are emitted even when incinerated.
[0095]
The present invention Of the Reester composition (F) is a variety of molded products, molding resins, sheet and film materials, paint resins, ink resins, toner resins, adhesive resins, medical materials, paper lamination, foamed resin materials In particular, it is useful as a packaging material and an adhesive.
[0096]
Examples of packaging materials include trays, cups, dishes, blisters, etc. as films, wrap films, food packaging, other general packaging, garbage bags, plastic bags, general standard bags, heavy bags, etc. Useful for.
[0097]
In addition, it is also useful as a blow-molded product for other uses, such as shampoo bottles, cosmetic bottles, beverage bottles, oil containers, etc., sanitary products, disposable diapers, sanitary products, and artificial kidneys for medical use. It is useful for germs, seed strings, agricultural multi-films, slow-acting agricultural chemicals and fertilizer coatings, bird nets, curing films, seedling pots, etc.
[0098]
In addition, fishery materials include fishing nets, laver culture nets, fishing lines, ship bottom paint, etc., and injection-molded products include golf tees, cotton swab cores, candy sticks, brushes, toothbrushes, syringes, dishes, cups, combs, It is useful for stationery items such as razor handles, tape cassettes, disposable spoons and forks, and ballpoint pens.
[0099]
In addition, paper lamination products include trays, cups, dishes, megaphones, etc., as well as binding tapes, prepaid cards, balloons, pantyhose, hair caps, sponges, cellophane tapes, umbrellas, goggles, plastic gloves, hair Caps, ropes, non-woven fabrics, tubes, foam trays, foam cushioning materials, cushioning materials, packing materials, cigarette filters and the like.
[0100]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example and a comparative example, this invention is not limited to these Examples at all. In the examples, “parts” or “%” are based on mass unless otherwise specified.
[0101]
The measurements performed in the examples are as follows.
(Molecular weight measurement)
It measured by the comparison with a standard polystyrene sample by the gel permeation chromatography measuring apparatus (Hereafter, it abbreviates as GPC. HLC-8020 by Tosoh Corporation, column temperature 40 degreeC, tetrahydrofuran solvent, flow rate 1 ml / min).
[0102]
(Thermal properties measurement)
Using a differential scanning calorimeter (hereinafter abbreviated as DSC; DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd.), a range of −100 to 200 ° C. was measured at a temperature rising rate of 10 ° C./min.
[0103]
(Proton nuclear magnetic resonance measurement (hereinafter abbreviated as 1H-NMR)
30 mg of measurement sample was mixed with chloroform-d (CDCl 3 ) It melt | dissolved in 0.5 mL, this was put into the glass ampule for NMR, and it measured at 25 degreeC with the 1H-NMR apparatus (JNM-LA300 by JEOL Ltd.).
[0104]
(Transparency measurement; hereinafter abbreviated as “haze”)
Polyester composition 3.8g and 12cm x 12cm square hollow polyethylene terephthalate (PET) film 200μm thick sandwiched by 100μm polyimide film and melted at 190-200 ° C, pressure 50kg / cm 2 Press for 1 minute. Thereafter, it was put on a water-cooled press for 5 minutes, taken out and left at room temperature for 24 hours. The obtained film was cut into 5 cm length × 5 cm width and measured with a turbidimeter (ND-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.).
[0105]
(DuPont impact strength test)
Using the DuPont impact strength measurement method of JIS K 5400, the weight of a constant weight was dropped and dropped, and the 50% fracture energy of the previously obtained film was determined according to the presence or absence of breakage. The striking portion with the film is made of steel, and is a smooth hemisphere (manufactured by Uesima Seisakusho) with a radius of 6.3 mm.
[0106]
(Bleed-out test and evaluation method)
The film obtained previously was kept at 35 ° C. and humidity 80 ° C. and left in a high temperature and humidity chamber PR-2F manufactured by Tabais Pack. And the thing which did not bleed out even if 200 days or more passed was described as (circle), and the thing which bleeded out was described as *.
[0107]
Reference Example 1 (Synthesis of Aliphatic Polyester B-1)
In a 50 L reactor equipped with a stirrer, a rectifier, and a gas introduction tube, 1 mol equivalent of sebacic acid (hereinafter abbreviated as SeA) and 1.4 mol of propylene glycol (hereinafter abbreviated as PG). An equivalent amount was charged, and the mixture was heated and stirred while being heated from 150 ° C. to 10 ° C. per hour under a nitrogen stream. The temperature was raised to 220 ° C. while distilling off the generated water, and after 2 hours, 100 ppm of titanium tetraisopropoxide was added as a transesterification catalyst, the pressure was reduced to 0.1 KPa, and the mixture was stirred for 8 hours, and GPC was used. An aliphatic polyester (B-1) having a number average molecular weight (hereinafter abbreviated as Mn) in terms of polystyrene of 35,000 and a weight average molecular weight (hereinafter abbreviated as Mw) of 63,000 was obtained.
[0108]
Reference Example 2 (Synthesis of Aliphatic Polyester B-2)
A 50 L reactor equipped with a stirrer, a rectifier, and a gas introduction tube was charged with 1 molar equivalent of SeA and 1.4 molar equivalent of PG, and heated from 150 ° C. to 10 ° C. per hour under a nitrogen stream. Stir with heating. While distilling off generated water, the temperature was raised to 220 ° C., and after 2 hours, 50 ppm of titanium tetrabutoxide was added as a transesterification catalyst, and the pressure was reduced to 0.1 KPa, followed by stirring for 3 hours. After the reaction, 2 parts of pyromellitic dianhydride (hereinafter abbreviated as PMDA) was added and stirred at 210 ° C. while reducing pressure at 0.1 KPa for 3 hours. 75,000 aliphatic polyester (B-2) was obtained.
[0109]
(Reference Example 3) (Synthesis of Aliphatic Polyester B-3)
In a 50 L reaction vessel equipped with a stirrer, a rectifier, and a gas introduction tube, 76 parts of succinic acid (hereinafter abbreviated as SuA) and 24 parts of adipic acid (hereinafter abbreviated as AA), dicarboxylic acid 1 mol equivalent of 1,4 butanediol (hereinafter abbreviated as 1,4BG) is charged and heated while increasing the temperature from 150 ° C. to 10 ° C. per hour in a nitrogen stream. Stir. The polyester obtained after the reaction was prepared in a 20% toluene solution, and 0.05 part of hexamethylene diisocyanate (hereinafter abbreviated as HMDI) was added to the polyester. Furthermore, 0.01 part of tin octoate was added to the polyester and stirred at 60 ° C. for 1 hour to obtain an aliphatic polyester (B-3) having an Mn of 51,000 and a weight average molecular weight Mw of 95,000. Obtained.
[0110]
Reference Example 4 (Synthesis of Aliphatic Polyester B-4)
In a 50 L reaction tank equipped with a stirrer, a rectifier, and a gas introduction tube, 1 mol equivalent of succinic acid (hereinafter abbreviated as SuA) and 1.4 mol of propylene glycol (hereinafter abbreviated as PG). An equivalent amount was added, and the mixture was heated and stirred while raising the temperature from 150 ° C. to 10 ° C. per hour under a nitrogen stream. While distilling off the generated water, the temperature was raised to 220 ° C., and after 2 hours, 150 ppm of titanium tetraisopropoxide was added as a transesterification catalyst, the pressure was reduced to 0.1 KPa and the mixture was stirred for 6 hours, and Mn was 18,000. An aliphatic polyester (B-4) having an Mw of 27,000 was obtained.
[0111]
(Reference Example 5) (Synthesis of Aliphatic / Aromatic Polyester B-5)
A 500 mL flask equipped with a stirrer, a rectifier, and a gas introduction tube was charged with 47 parts of AA, 53 parts of TPA, and 1.4 mole equivalent of 1,4BG with respect to 1 mole equivalent of dicarboxylic acid. The mixture was heated and stirred while the temperature was raised from 150 ° C. to 10 ° C. per hour. The temperature was raised to 220 ° C. while distilling off the water produced, and after 2 hours, 100 ppm of titanium isopropoxide was added as a transesterification catalyst, and the pressure was reduced to 0.1 KPa and the mixture was stirred for 7 hours. An aliphatic / aromatic polyester (B-5) having a Mn of 48,000 in terms of polystyrene using GPC and a Mw of 103,000 was obtained.
[0112]
Reference Example 6 (Synthesis of Aliphatic Polyester B-6)
In a 10 L reaction vessel equipped with a stirrer, a rectifier, and a gas introduction tube, “Empole 1062” (a dimer acid that is a dimer of an aliphatic unsaturated carboxylic acid having 18 carbon atoms and partially hydrogenated by Cognis; Hereinafter, abbreviated as DAH.) DAH 66 parts, 1,6-cyclohexanedicarboxylic acid (manufactured by Eastman Chemical Co .; hereinafter abbreviated as CHDA) 34 parts, 1 mol equivalent of dicarboxylic acid, 0.9 mol An equivalent amount of ethylene glycol (hereinafter abbreviated as EG) and 0.5 molar equivalent of 1,6-hexanediol (hereinafter abbreviated as 1,6HD) were charged, and the temperature was increased from 150 ° C. to 1 hour under a nitrogen stream. The mixture was heated and stirred while the temperature was raised by 7 ° C. While distilling off generated water, the temperature was raised to 220 ° C., and after 2 hours, 50 ppm of tributyltin oxide was added as a transesterification catalyst, and the pressure was reduced to 0.1 KPa, followed by stirring for 2 hours. After the reaction, the polyester obtained after the reaction was prepared in a 20% toluene solution, and 0.05 part of HMDI was added to the polyester. Further, 0.01 part of tin octoate was added to the polyester and stirred at 60 ° C. for 1 hour to obtain a highly viscous liquid aliphatic polyester (B-6) having an Mn of 25,000 and an Mw of 55,000. Obtained.
[0113]
[Table 1]
[0114]
[Table 2]
[0115]
(Example 1) (Synthesis of polyhydroxycarboxylic acid copolymer C-1)
50 parts of aliphatic polyester (B-1) and 50 parts of polylactic acid (Mw 170,000, Mn 92,000; hereinafter abbreviated as PLA1) are placed in a separable flask equipped with a stirring blade at 210 ° C. Melted. Thereafter, 100 ppm of titanium tetrabutoxide was added at 200 ° C. in a nitrogen atmosphere, and the reaction was carried out at a reduced pressure of 0.1 KPa for 5 hours. After completion of the reaction, 500 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-1) having an Mn of 52,000 and an Mw of 108,000. The obtained C-1 was remarkably higher than the molecular weight after melting, and the properties were solid. Moreover, it showed the single peak by GPC measurement and confirmed that it was a copolymer.
[0116]
(Example 2) (Synthesis of polyhydroxycarboxylic acid copolymer C-2)
10 parts of aliphatic polyester (B-1) and 90 parts of PLA1 were placed in a separable flask equipped with a stirring blade and melted at 210 ° C. Thereafter, 100 ppm of titanium tetrabutoxide was added at 200 ° C. in a nitrogen atmosphere, and the mixture was reacted at a reduced pressure of 0.05 KPa for 5 hours. After completion of the reaction, 300 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-2) having Mn of 70,000 and Mw of 126,000. The obtained C-2 was remarkably higher than the molecular weight after melting, and the properties were solid. Moreover, it showed the single peak by GPC measurement and confirmed that it was a copolymer.
[0117]
The obtained C-2 was dried and then hot pressed at a temperature of 190 ° C. to prepare a 200 μm film. This film had a haze of 15%, a DuPont impact strength of 0.51 J, a storage elastic modulus at 25 ° C. of 1.8 GPa, and a bleed-out evaluation of “◯”.
[0118]
(Example 3) (Synthesis of polyhydroxycarboxylic acid copolymer C-3)
40 parts of aliphatic polyester (B-2) and 60 parts of polylactic acid (Mw87,000, Mn42,000; hereinafter abbreviated as PLA2) are placed in a separable flask equipped with a stirring blade at 210 ° C. Melted. Thereafter, 80 ppm of titanium tetrabutoxide was added at 200 ° C. in a nitrogen atmosphere, and the mixture was reacted at a reduced pressure of 0.3 KPa for 5 hours. After completion of the reaction, 500 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-3) having an Mn of 58,000 and an Mw of 186,000. The obtained C-3 was remarkably higher than the molecular weight after melting, and the properties were solid. Moreover, it showed the single peak by GPC measurement and confirmed that it was a copolymer.
[0119]
(Example 4) (Synthesis of polyhydroxycarboxylic acid copolymer C-4)
30 parts of aliphatic polyester (B-3) and 70 parts of polycaprolactone (Mw 52,000, Mn 32,000; hereinafter abbreviated as PCL) were placed in a separable flask equipped with a stirring blade at 170 ° C. Melted. Thereafter, 80 ppm of titanium tetrabutoxide was added at 180 ° C. in a nitrogen atmosphere, and the mixture was reacted at a reduced pressure of 0.5 KPa for 6 hours. After completion of the reaction, 300 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-4) having an Mn of 44,000 and an Mw of 83,000. The obtained C-4 was remarkably higher than the molecular weight after melting, and the properties were semi-solid. Moreover, it showed the single peak by GPC measurement and confirmed that it was a copolymer.
[0120]
Example 5 (Synthesis of polyhydroxycarboxylic acid copolymer C-5)
50 parts of aliphatic polyester (B-4) and 50 parts of polylactic acid (Mw 160,000, Mn 85,000; hereinafter abbreviated as PLA3) were placed in a separable flask equipped with a stirring blade at 210 ° C. Melted. Thereafter, 120 ppm of titanium tetrabutoxide was added at 200 ° C. in a nitrogen atmosphere, and the reaction was carried out at a reduced pressure of 0.2 KPa for 10 hours. After completion of the reaction, 300 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-5) having Mn of 27,000 and Mw of 41,000. Moreover, it showed the single peak by GPC measurement and confirmed that it was a copolymer.
[0121]
(Example 6) (Synthesis of polyhydroxycarboxylic acid copolymer C-6)
90 parts of the aliphatic / aromatic polyester (B-5) and 10 parts of polylactic acid (Mw 143,000, Mn 80,000; hereinafter abbreviated as PLA 4) are placed in a separable flask equipped with a stirring blade. Melted at 195 ° C. Thereafter, 50 ppm of titanium isopropoxide was added at 190 ° C. in a nitrogen atmosphere, and the mixture was reacted at a reduced pressure of 1.3 KPa for 10 hours. After completion of the reaction, 300 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-6) having an Mn of 46,000 and an Mw of 105,000. The obtained C-6 was remarkably high compared to the molecular weight after melting, and the properties were solid.
[0122]
(Example 7) (Synthesis of polyhydroxycarboxylic acid copolymer C-7)
10 parts of aliphatic polyester (B-6) and 90 parts of polylactic acid (Mw 250,000, Mn 160,000; hereinafter abbreviated as PLA5) are placed in a separable flask equipped with a stirring blade at 210 ° C. Melted. Thereafter, 500 ppm of titanium tetraisopropoxide was added at 200 ° C. in a nitrogen atmosphere, and the mixture was reacted at a reduced pressure of 2.0 KPa for 4 hours. After completion of the reaction, 300 ppm of ethylhexanoic acid phosphate was added to obtain a polyhydroxycarboxylic acid copolymer (C-7) having an Mn of 36,000 and an Mw of 115,000. The obtained C-7 was remarkably high compared to the molecular weight after melting, and the properties were solid.
[0123]
(Comparative Example 1)
50 parts of aliphatic polyester (B-1) and 50 parts of PLA1 were placed in a separable flask equipped with a stirring blade and melted at 210 ° C. Thereafter, 100 ppm of titanium tetrabutoxide was added at 200 ° C. in a nitrogen atmosphere, and the reaction was carried out at atmospheric pressure for 8 hours. After completion of the reaction, 350 ppm of ethylhexanoic acid phosphate was added to obtain a polyester composition (C-8) containing a polyhydroxycarboxylic acid having an Mn of 26,000 and an Mw of 46,000 and an aliphatic polyester. The obtained C-8 was remarkably lower than the molecular weight after melting, and its properties were a highly viscous liquid. C-8 contained a large amount of lactide.
[0124]
(Comparative Example 2)
70 parts of aliphatic polyester (B-2) and 30 parts of PLA4 were placed in a separable flask equipped with a stirring blade and melted at 220 ° C. Then, it was made to react at 195 degreeC and nitrogen atmosphere and atmospheric pressure for 5 hours. After completion of the reaction, 50 ppm of ethylhexanoic acid phosphate was added to obtain a polyester composition (C-9) containing a polyhydroxycarboxylic acid having Mn of 38,000 and Mw of 70,000 and an aliphatic polyester. The obtained C-9 was remarkably low compared to the molecular weight after melting, and the properties were a highly viscous liquid. C-9 contained a large amount of lactide.
[0125]
The production results of the polyhydroxycarboxylic acid copolymers obtained in Examples 1 to 7 are shown in Table 3, Table 4, Comparative Example 1, and Comparative Example 2 in Table 5.
[0126]
The molecular weights of the polyhydroxycarboxylic acid copolymers obtained in Examples 1 to 7 were larger than the molecular weight after melting, whereas the molecular weights of Comparative Examples 1 and 2 were after melting. The molecular weight was extremely small compared to the molecular weight, and a large amount of lactide was contained. Moreover, the mass ratio of the polyhydroxycarboxylic acid (A) and the polyester (B) of the polyhydroxycarboxylic acid-based copolymer obtained in Example 1 to Example 7 determined by NMR spectrum measurement is polyhydroxycarboxylic acid. The amount was substantially the same as the charged amount of (A) and polyester (B). On the other hand, the mass ratio of the polyhydroxycarboxylic acid (A) and the polyester (B) in the compositions obtained in Comparative Example 1 and Comparative Example 2 determined by NMR spectrum measurement was as follows. The amount of polylactic acid depolymerization was proceeding significantly different from the amount charged in B).
[0127]
[Table 3]
[0128]
[Table 4]
[0129]
[Table 5]
[0130]
(Example 8) (Polyester composition P-1 and film production)
After drying 100 parts of PLA1 and 10 parts of C-1, each was kneaded for 10 minutes while heating at 190 ° C. using a Laboplast mill mixer manufactured by Toyo Seiki Co., to obtain a polyester composition P-1. The obtained P-1 was hot-pressed at a temperature of 190 ° C. to produce a 200 μm film.
[0131]
(Example 9) (Polyester composition P-2 and film production)
After drying 100 parts of PLA4 and 10 parts of C-3, each was kneaded while heating at 200 ° C. using a lab plast mill twin screw extruder manufactured by Toyo Seiki Co., to obtain a polyester composition P-2. . Further, it was pelletized with a single screw extruder manufactured by Ikegai. The obtained P-2 pellet was hot-pressed at a temperature of 190 ° C. to produce a 200 μm film.
[0132]
(Example 10) (Polyester composition P-3 and film production)
After drying 100 parts of PLA4 and 10 parts of C-4, each was kneaded for 10 minutes while heating at 180 ° C. using a Laboplast mill mixer manufactured by Toyo Seiki Co., Ltd. to obtain a polyester composition P-3. The obtained P-3 was hot pressed at a temperature of 190 ° C. to produce a 200 μm film.
[0133]
(Example 11) (Polyester composition P-4 and film production)
After 100 parts of PLA1 and 30 parts of C-5 were dried, the mixture was melted and stirred in a 20 L reactor manufactured by Kobe Steel, and then fed into a static mixer SMX manufactured by Sumitomo Heavy Industries Co. -4 was obtained. Further, P4 was pelletized by a twin-screw extruder manufactured by Toshiba Machine. The obtained P-4 pellet was hot-pressed at a temperature of 190 ° C. to produce a 200 μm film.
[0134]
(Example 12) (Polyester composition P-5 and film production)
After drying 100 parts of PLA4 and 10 parts of C-6, each was kneaded for 10 minutes while heating at 180 ° C. using a lab plast mill mixer manufactured by Toyo Seiki Co., Ltd. to obtain a polyester composition P-5. The obtained P-5 was hot-pressed at a temperature of 195 ° C. to produce a 200 μm film.
[0135]
(Example 13) (Polyester composition P-6 and film production)
After drying 100 parts of PLA4 and 15 parts of C-7, each was kneaded while heating at 200 ° C. using a lab plast mill twin screw extruder manufactured by Toyo Seiki Co., to obtain a polyester composition P-6. . Further, it was pelletized with a single screw extruder manufactured by Ikegai. The obtained P-6 pellet was hot-pressed at a temperature of 195 ° C. to produce a 200 μm film.
[0136]
(Comparative Example 3) (Polyester composition P-7 and film production)
After drying 100 parts of PLA1 and 10 parts of C-8 produced in Comparative Example 1, each was kneaded while heating at 190 ° C. using a Laboplast Mill mixer manufactured by Toyo Seiki Co. to obtain a polyester composition P-7. Got. The obtained P-7 was hot pressed at a temperature of 190 ° C. to produce a 200 μm film.
[0137]
(Comparative Example 4) (Polyester composition P-8 and film production)
100 parts of PLA1 and 10 parts of C-9 produced in Comparative Example 2 were dried and then kneaded while heating at 190 ° C. using a Laboplast Mill mixer manufactured by Toyo Seiki Co. to obtain a polyester composition P-8. Got. The obtained P-8 was hot pressed at a temperature of 195 ° C. to produce a 200 μm film.
[0138]
(Comparative Example 5) (PLA1 film production)
After PLA1 was dried, it was hot pressed at a temperature of 195 ° C. to produce a 200 μm film.
[0139]
Tables 6 to 8 show the haze measurement, the DuPont impact strength measurement, the storage elastic modulus at 25 ° C. from the DMA measurement, and the bleed out evaluation for the films obtained in Examples 8 to 13 and Comparative Examples 3 and 4. It was.
[0140]
[Table 6]
[0141]
[Table 7]
[0142]
[Table 8]
[0143]
The present invention Of the Polyester compositions containing a rehydroxycarboxylic acid copolymer as an impact resistance imparting agent are polylactic acid alone or atmospheric pressure as shown in Examples 8 to 14 and Comparative Examples 3 to 5. It has been found that it has an impact resistance 2 to 7 times that of the composition obtained below, and has excellent transparency, flexibility and bleed-out suppression effect.
[0144]
(Example 15) (Degradability test)
The polyester composition obtained in Examples 1 to 14 was made into a paste or a film was sandwiched between wire meshes and embedded in electric compost kept at 45 ° C. When the wire mesh was taken out after 30 days, the polyester composition hardly remained in its original form. Further, after 60 days, it could not be confirmed. From this, it was found that the polyester composition obtained in the present invention is also excellent in degradability.
[0145]
【The invention's effect】
According to the present invention, polyhydroxycarboxylic acid and polyester When Using Polyhydroxycarboxylic acid copolymer produced by , Against polyhydroxycarboxylic acids By blending, Bleed-out with excellent flexibility and impact resistance while maintaining heat resistance The Can be suppressed The More transparent In outstanding Polyester composition Can be provided.
[Brief description of the drawings]
1 shows a chart of GPC measurement results of a polyhydroxycarboxylic acid copolymer obtained in Example 1. FIG.

Claims (9)

  1. A polyhydroxycarboxylic acid (A) having a weight average molecular weight of 5,000 to 400,000 and a polyester (B) comprising a dicarboxylic acid having a weight average molecular weight of 5,000 to 200,000 and a diol are melted and then transesterified A polyester composition comprising an impact resistance imparting agent comprising a polyhydroxycarboxylic acid copolymer obtained by adding a catalyst (C) and causing a transesterification reaction under reduced pressure , and a polyhydroxycarboxylic acid Thing .
  2. The polyester composition according to claim 1, wherein the polyhydroxycarboxylic acid copolymer is obtained by reacting at a reduced pressure of 5,000 Pascals or less.
  3. The polyhydroxycarboxylic acid copolymer, polyester composition according to claim 1 or 2 is obtained by reacting a reaction temperature of 1 00 to 280 ° C..
  4. The transesterification catalyst (C) is represented by Ti (OC n H 2n + 1 ) 4 (wherein n represents an integer of 1 to 8). A polyester composition as described in 1.
  5. The polyester composition according to any one of claims 1 to 4, wherein the polyhydroxycarboxylic acid (A) is polylactic acid.
  6. The polyester (B) comprising the dicarboxylic acid and the diol is an aliphatic polyester comprising an aliphatic dicarboxylic acid and an aliphatic diol, or an aliphatic / aromatic polyester comprising an aliphatic / aromatic dicarboxylic acid and an aliphatic diol. The polyester composition according to any one of claims 1 to 5.
  7. The polyhydroxycarboxylic acid (A) and the polyester (B) is a mass ratio (A) :( B) = 99 : 1~20: 80 polyester according to any one of claims 1 to 6 which is a ratio of Composition .
  8. The polyester composition according to any one of claims 1 to 7, wherein the polyhydroxycarboxylic acid copolymer has a weight average molecular weight of 10,000 or more and a glass transition temperature of 60 ° C or less.
  9. The polyester composition according to any one of claims 1 to 8, wherein the polyhydroxycarboxylic acid copolymer has a storage elastic modulus at 20 ° C of 2.5 gigapascal or less.
JP2001231608A 2001-07-31 2001-07-31 Polyester composition Expired - Fee Related JP4807544B2 (en)

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