KR980009313A - Method for producing aliphatic copolymerized polyester - Google Patents

Abstract

The present invention relates to a biodegradable aliphatic copolymer polyester which can be used for disposable films, fibers, nonwoven fabrics and injection molding processes, and which can be decomposed by microorganisms at the time of disposal, And to provide a biodegradable polymer material having high melt strength and melt viscosity.

In order to achieve the above object, the present invention provides a process for esterifying a mixture composed of an acid component composed of succinic acid and the like, a diol component of a mixed component, and a polyfunctional compound having three or more OH groups or alcohol groups, The aliphatic polyester copolymer prepared in this way is used as a film, etc., and is excellent in biodegradability such as being rapidly decomposed into a harmless substance when it is used after disposal. It has a castle.

Description

Method for producing aliphatic copolymerized polyester

The present invention relates to a process for producing an aliphatic copolymerized polyester having a biodegradable function and, more particularly, to a process for producing an aliphatic copolymerized polyester having a high degradability and a high melt strength.

Conventional general-purpose plastics have excellent mechanical properties, chemical resistance and durability and are widely used in everyday life. However, they have a disadvantage that they can not be returned to nature when they are disposed of after use. Disposable packaging materials, which are rapidly increasing in demand in recent years, are often left untouched because they are not recovered smoothly despite their high consumption. Agricultural films are difficult to recover completely and are buried in the soil, which causes a lot of crop growth. As environmental pollution caused by plastic waste becomes a social problem, development of decomposable resin which is decomposed automatically at the time of disposal after use is actively promoted in order to protect the environment.

The degradable resin is biodegradable, which can be fully decomposed and assimilated by nature, by water and microorganisms when it is classified according to its decomposition mechanism, and the biodegradability that the starch or metal compound added to the matrix itself decomposes or decomposes, It can be divided into photodegradability that is molecular designed to digest and absorb by the microorganism because the main chain of polymer is cut by ultraviolet rays of 290 ~ 320nm wavelength of light and the molecular weight is lowered.

Biodegradable plastics can be classified into a production type produced by microorganisms, a natural product type using natural polymers present in nature, and an active polymer type easy to be degraded by microorganisms. Of the synthetic polymers, only aliphatic polyester is 100 It is known that% complete decomposition is possible.

Aliphatic polyesters are produced by polycondensation of glycols and dicarboxylic acids as raw materials, ring-opening polymerization of cyclic monomers, transesterification of polyesters, etc. They are excellent in physical properties and processability, capable of controlling decomposition mechanisms, And in the 1960s American Cyanamide developed an absorbable surgical suture made of polyglycolide under the trade name "DEXON". In recent years, polylactic acid based polymer materials have also been developed. Union Carbide has commercialized biodegradable resins under the trade name "TONE" for polycaprolactone. The ring-opening polymerization of the cyclic ester monomer is mainly used with 4, 5, 6, and 7-membered rings and lactones, and it is generally known that the molecular weight can be increased to such an extent that molding can be performed. However, polyglycolide or polylactide, which has been used for medicines so far, is not suitable as a general polymeric material because of poor physical properties and economical efficiency, and polycaprolactone has a low melting point and is known to have a problem in thermal stability and dimensional stability have.

The crystalline polymer synthesized by ring opening polymerization of polyglycolide in the presence of a catalyst has a high molecular weight and a high glass transition temperature but is hard and has low solubility. The lactone polymer is flexible and has excellent molecular weight and solubility However, there is a problem that the glass transition is low. Efforts have been made to solve the disadvantages of each homopolymer by copolymerizing glycolide and various lactones in the presence of a catalyst, or by synthesizing a block copolymer of? -Caprolactone and another lactone.

On the other hand, composite materials using natural materials such as starch and cellulosic are also actively researched. In the field of microfibers, polyhydroxybutyrate is filled with cellulose, or polyvinylpyrrolidone An attempt has been made to have biodegradability by introducing biodegradability. The method of filling the universal polymer with starch is one of the most useful methods because the manufacturing method is easy and the existing forming processing apparatus can be used as it is. However, since the hydrophilic starch is not compatible with the hydrophobic general purpose polymer, However, the introduction of such natural materials is difficult to obtain the uniformity of the quality of the produced products, and thus, many problems are encountered in commercialization.

On the other hand, improper disposal of municipal waste buried in landfills and increase of non-degradable materials such as plastics in municipal waste not only increases landfill costs but also drastically reduces available landfills. Plastics that can be reused in the trash are the most desirable way to recycle, but it is difficult to recycle plastics such as diapers, sanitary towels, and garbage bags because they are difficult to collect. In recent years, there has been an active trend toward reducing the volume of solid waste to be landfilled by composting solid waste that can not be recycled, or converting waste to fertilizer and commercializing the solid waste. However, the tobacco produced by the composting of municipal waste has not yet overcome the problem of many plastic products remaining in a circular shape without being decomposed during the composting process.

In view of the above problems, the present inventors have made polyester copolymers having aliphatic bivalent alcohols and aliphatic dicarboxylic acids as main components and having biodegradability, as well as being capable of composting and having excellent molding processing characteristics.

In other words, the present invention can improve the melt viscosity and melt strength by significantly improving the molecular weight of an aliphatic polyester which is used as a paint or an adhesive, unlike a high melting point aromatic polyester such as polyethylene terephthalate, The present invention relates to an aliphatic polyester copolymer which can be used for producing a blown film.

U.S. Patent Nos. 4219527 and 4912167 disclose the case of using a reactive compound capable of forming a crosslink to make polyethylene terephthalate or polybutylene terephthalate resin capable of blow molding, And a diol component are all used as an aliphatic compound, there is no example in which a blown film or the like is produced. Even if an aliphatic polycondensation reaction is performed as an acid component and a glycol component, a melt viscosity sufficient to impart excellent film formability and processability It is difficult to obtain the melt strength and even if the film is formed, the process workability and the mechanical properties of the molded product become poor.

On the other hand, a method of increasing the molecular weight is generally used as a method of improving the mechanical properties and the melt strength. However, if the molecular weight is excessively increased, the melt viscosity becomes very high, which makes it very difficult to pass through the extruder during processing, so the polymer design is very important. The melt strength of a polymer is usually determined by the elasticity of the polymer melt. The factors affecting elasticity include molecular weight distribution, degree of branch, and additives. Generally, the larger the molecular weight, the larger the branching degree, and the more the entanglement of the polymer melt, the more elasticity increases. In the case of polyester, it is also known that particles such as stearic acid or talc or silica have an effect of improving the melt strength. Other factors that have a great effect on the molding process include the rate of crystallization and the crystallization rate and crystallization of the polymer may be controlled depending on the molding process.

In Japanese Patent Nos. 92-189822 and 92-189823, aliphatic dicarboxylic acids and aliphatic divalent glycols are subjected to an esterification reaction, and after the condensation polymerization reaction, the isocyanate compound is further reacted to increase the molecular weight, thereby improving the melt viscosity and the melt strength However, it did not reach satisfactory level.

In order to accomplish the object described above, the present invention provides a process for producing a polylactic acid by a process comprising the steps of subjecting an aliphatic alcohol and a carboxylic acid having a specific structure as a main component to an esterification reaction, A method of producing a polyester having a melt viscosity and a melt strength.

Hereinafter, this description will be described in detail.

The present invention specifically relates to an acid component comprising succinic acid or an ester compound thereof, and 70 to 95% by weight of one component selected from 1,4-butanediol and ethyl glycol, and the remainder comprising 1,6-hexanediol, 2 , 2-dimethyl-1,3-propanediol, 1,6-cyclohexanedimethanol, and a polyfunctional compound having three or more hydroxyl groups or alcohol groups Is subjected to an esterification reaction, and then the organosilicon compound represented by the following general formula (I) is added together with other additives to polycondensate the mixture.

In the present invention, succinic acid is used as an acid component. It is possible to use a succinic acid ester compound instead of succinic acid, and examples of the succinic acid ester compound include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl Seishin nate, and diacetyl citrate. The reaction molar ratio of succinic acid or succinic anhydride or succinic acid ester compound to the diol component is preferably 1: 1 to 1: 2. More preferably 1: 1.1 to 1: 1.7 in terms of reactivity and physical properties and color tone of the resultant polymer.

The diol component comprises 70 to 95 mol% of one component selected from among 1,4-butanediol and ethylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, And one component selected from 6-cyclohexane dimethanol is composed of 5 to 30% water. In the case of aliphatic polyesters synthesized by the combination of succinic acid and 1,4-butanediol or a combination of succinic acid and ethylene glycol, the crystallization rate is very high and the bluish film processability is poor and it is difficult to obtain a transparent film. Accordingly, it is possible to control the crystallization rate of the aliphatic copolymerized polyester formed by using one component selected from 1,4-butanediol and ethylene glycol as the main component and the other diol component as the comonomer besides the main component, and it is possible to control the crystallization speed of the film, And processing can be ensured. At this time, it is preferable that the content of the comonomer is in the range of 5 to 30 mol% based on the total diol component. When the content of the comonomer is less than 5 mol%, the control of the crystallization rate of the aliphatic polyester formed is not smooth and the transparency of the formed film and formed film becomes poor. When the content of the comonomer is more than 30 mol%, the crystallization rate of the condensation-polymerized aliphatic copolymerized polyester becomes very slow, and the processability of the blown film becomes very poor, and the melting point is also inadequate for film applications.

Examples of the trifunctional or higher polyfunctional compound include trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, trimellitic acid, trimellitic acid anhydride, benzene Tetracarboxylic acid, benzetetracarboxylic anhydride and the like can be used. The molecular weight of the polymer produced by a small amount copolymerization reaction of a compound having three or more functionalities is rapidly increased, and thus the melt viscosity and the melt strength are greatly improved. At this time, it is important that the compound having three or more functionalities is subjected to a copolymerization reaction within a range of 0.01 to 1 mol%. When a compound having three or more functionalities is copolymerized in an amount exceeding 1 mol%, the reaction proceeds in a very long time and a polymer can be obtained in a high molecular weight. However, since the degree of crosslinking is rapidly increased, a gel is formed, Polymer. When the content is less than 0.01 mol%, the effect of use is hardly observed.

In the esterification or transesterification reaction, the reaction temperature is preferably 220 캜 or lower, which is suitable for minimizing the formation of by-products and thermal decomposition. After completion of the ester reaction, it is important to add the organosilicon compound to the ester reaction product in an amount of 0.1 to 5 wt% to proceed the condensation polymerization reaction. The organosilicon compound not only exhibits properties as a defoaming agent in the condensation polymerization reaction but also exhibits effects such as hydrolysis resistance of the aliphatic copolymerized polyester formed by condensation polymerization or prevention of change in the mechanical properties of the film due to ultraviolet rays. When the amount of the organosilicon compound used is more than 5% by weight based on the esterification reaction product, the reaction time during the condensation polymerization is considerably retarded, and the film processing property is deteriorated, and the biodegradability is drastically lowered. The silicone organic compound used in the present invention has a viscosity of about 100 cs to 50,000 cs, which is advantageous in the condensation polymerization. When the viscosity is less than 100 cs, the heat resistance of the organosilicon compound is very poor and the condensation reaction is inhibited. When the viscosity exceeds 50,000 cs, the gel is formed even if the silicone compound itself has a slight decomposition during condensation polymerization, The processability is badly affected when the film is formed into a polymerized aliphatic copolymerized polyester.

As the polycondensation catalyst to be used in the present invention, a tin compound system or a titanium compound system is mainly used. Examples of the tin compound include starch oxide such as oxidized starch, oxidized zeolite, and the like, tin chloride, stannous chloride, There may be mentioned organic tin compounds such as halide of pentaerythritol, pentaerythritol dicarboxylate, dibutyl tin oxide, monobutyl tin oxide, monobutylhydroxy tin oxide, dibutyltin dibromide, tetraphenyltin and tetrabutyltin, Titanate, tetramethyl titanate, tetraisopropyl titanate, tetra (2-ethylhexyl) titanate and the like can be used. The amount of the polymerization catalyst to be used in the present invention is suitably in the range of 0.01 to 0.1 mol% relative to the succinic acid component. At this time, when the amount of the catalyst used is too large, discoloration of the polymer occurs severely, and when the amount is too small, the reaction rate is slowed down.

As the thermal stabilizer in the present invention, phosphorus compounds can be used, and examples thereof include phosphoric acid, monomethylphosphoric acid, trimethylphosphoric acid, tributylphosphoric acid, trioctylphosphoric acid, monophenylphosphoric acid, triphenylphosphoric acid and its derivatives, Phosphoric acid, trimethylphosphoric acid, triphenylphosphoric acid, and the like are more effective. Among these, phosphoric acid, trimethylphosphoric acid, and triphenylphosphoric acid are more effective. The amount of the phosphorus compound as the heat stabilizer is 1.0 × 10 ⁷ -1.0 × 10 ⁸ mol / g oligomer, more preferably 0.5 × 10 ^-6 to 1.5 × 10 ⁸ mol / mol, relative to the oligomer obtained by the esterification or transesterification reaction. Gram oligomers.

In the present invention, in order to obtain a high molecular weight aliphatic copolymer polyester having a high melt strength and a high melt strength, it is important to perform condensation polymerization under high vacuum conditions, and the reaction temperature is effectively 240 to 260 ° C. When the reaction temperature is less than 240 ° C, the rate of condensation polymerization is very slow and it is difficult to obtain a desired high molecular weight polymer. When the temperature exceeds 260 ° C, the thermal decomposition becomes rather severe and the obtained polymer tends to have poor physical properties and color tone.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.

The intrinsic viscosity (dl / g) of the copolymerized polyester was measured by dissolving it in an orthochlorophenol solution at 35 ° C, and the crystalline melting point was analyzed by differential thermal calorimetry. The film for measuring mechanical properties such as tensile strength, The tensile strength (kg / cm 2) and elongation at break (%) were measured according to ASTM D-412. The elongation at break of the film was maintained at 30 ° C and 80% relative humidity After leaving the film sample in a constant temperature and humidity chamber, tensile strength and fracture toughness were measured and evaluated. The turbidity of the film was evaluated by using Hazemmeter according to ASTM D1003, and the haze value of the film was higher. The biodegradability of the produced polyester was also measured according to ASTM G-21-70 and Composting. The measurement procedure of ASTM G2l-70 is as follows. A sample film was placed on agar solid medium, and a mixed amount of Aspergillus niger, Henny sylum flavicollis, Dictyardema spp., And Pluralia flurans was dispersed on the sample film, and after 2 to 4 weeks, the degree of mold growth was checked If 10% or less of the specimen area is 1, 10-30%, 2, 30-60% is 3, and 60% or more is 4. The measurement procedure of the degradation acceleration evaluation method is as follows. The medium is prepared as shown in Table 1 in accordance with the composition ratio of the waste generated in the domestic market. And the degree of degradation was evaluated by measuring the weight loss of the sample film.

[Table 1] Composition ratio of waste for compost

[Table 2] Internal environmental components of the Composition method

The abbreviations used in the examples and comparative examples of the present invention are defined as follows.

[Example 1]

1.372 g (11.615 moles) of SA, 1,070 g (11.618 moles) of BD, 343 g (2.902 moles) of HD and 4 g (0.033 mole) of TME were charged into a reactor equipped with a stirrer and a condenser, The temperature was raised to 120 ° C and the temperature was raised to 210 ° C over 120 minutes while stirring. At this time, the generated water as a byproduct was completely drained out through a condenser, resulting in 2,480 g of esterification reaction product. Subsequently, 25 g of the silicone compound S-1 having a viscosity of 200 cs and 1.70 g of TBT as a catalyst were charged, and the pressure inside the tube was gradually reduced to 0.5 mmHg over 45 minutes. While the temperature was raised to 245 deg. C, The stirring was stopped and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain the desired aliphatic copolymerized polyester. The obtained resin was used for the production of blown film through hot air drying. The film was manufactured using BLAKE-UP RAT1O = 4, TAKE-UP using HAEKE's "RHEOCORD 90" blown film processing equipment having a hollow die diameter of 25 mm A film having a thickness of about 30 탆 was obtained by setting SM = 20 mm / min, SCREW SPEED = 9 rpm and barrel temperature conditions of 140 캜, 150 캜, 150 캜 and 150 캜. The tensile strength, And the results are shown in Table 3. < tb > < TABLE >

[Comparative Example 1]

1,372 g (11.618 moles) of SA and 1,338 g (14.525 moles) of BD were charged into a reactor equipped with a stirrer and a condenser, and the temperature inside the reactor was raised from room temperature to 120 DEG C over 20 minutes. At this time, the generated water as a byproduct was completely drained out through a condenser, resulting in 2,425 g of the esterification reaction product. Subsequently, the pressure in the pipe was gradually reduced to 0.5 mmHg over 45 minutes, and the stirring reaction was continued for 180 minutes while raising the temperature in the pipe to 245 DEG C. Then, stirring was stopped, and nitrogen was injected into the pipe, The desired aliphatic copolymerized polyester was obtained by discharging. The obtained resin was used to produce a blown film through hot air drying. The film was produced by using a HAAKE "RHEOCORD 90" blown film processing equipment having a hollow die diameter of 25 mm, BLOW-UP RATIO = 4, TAKE-UP SPFFD = 20 mm / min, SCREW SPEED = 9 rpm, and a barrel temperature condition of 140 캜, 150 캜, 150 캜 and 150 캜, and a tensile strength and film HAZE measurement result and the obtained resin The product properties are shown in Table 3.

[Comparative Example 2]

Table 3 shows the physical properties of the resulting resin and film, except that the condensation reaction was carried out without introducing the silicone compound 5-1 after the esterification reaction in Example 1. The results are shown in Table 3.

[Comparative Example 3]

1,372 g (11.615 mol) of SA, 1338 g (14.525 mol) of BD, 51.5 g (0.436 mol) of HD and 4 g (0.033 mol) of TME were charged into a reactor equipped with a stirrer and a condenser, The temperature was raised to 120 deg. C and the temperature was raised to 210 deg. C over 120 minutes with stirring. At this time, water as a byproduct, which was generated, was completely drained out through a condenser. As a result, 2,440 g of an esterification reaction product was obtained. Subsequently, 25 g of the silicone compound S-1 having a viscosity of 200 cs and 1.70 g of TBT as a catalyst were added thereto, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes. While the temperature in the tube was raised to 245 캜, The stirring was stopped and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain the desired aliphatic copolymerized polyester. The obtained resin was used for blown film production by hot air drying. The production of the film was carried out by using a "RHEOCORD 90" blown film processing equipment of HAAKE having a hollow die diameter of 25 mm, BLOW-UP RATIO = 4, TAKE-UP A film of about 30 μm was obtained with SPFFD = 20 mm / min, SCREW SPEED = 9 gm, and barrel temperature conditions of 140 ° C., 150 ° C., 150 ° C. and 150 ° C. The tensile strength, The physical properties of the resulting resin were evaluated and are shown in Table 3.

[Comparative Example 4]

In Example 1, the esterification reaction was carried out using 6309 (5.331 mol) instead of 343 g (2.902 mol) of HD, and the resulting esterification reaction product was 2,532 g. Subsequently, 28 g of the silicone compound S-1 having a viscosity of 200 cs and 1.7 g of TBT as a catalyst were charged, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, while the temperature was raised to 245 캜 for 120 minutes After the stirring reaction, the stirring was stopped, and nitrogen was injected into the tube, and the polymer was pressed and discharged to obtain the desired aliphatic copolymerized polyester. The obtained resin was used for blown film production by hot air drying. The production of the film was carried out by using a "RHEOCORD 90" blown film processing equipment of HAAKE having a hollow die diameter of 25 mm, BLOW-UP RATIO = 4, TAKE-UP A film having a thickness of about 30 탆 was obtained at SPFFD = 20 mm / min, SCREW SPEED = 9 rpm and barrel temperature conditions of 140 캜, 150 캜, 150 캜 and 150 캜. The physical properties of the resin were evaluated and shown in Table 3.

[Comparative Example 5]

The procedure of Example 1 was repeated except that 16.9 g (0.139 mol) of TME was used in the esterification reaction. The results are shown in Table 3.

[Comparative Example 6]

The procedure of Example 1 was repeated except that the silicone compound S-1 was used in an amount of 148 g instead of 25 g in the condensation polymerization reaction, and the results are shown in Table 3.

[Example 2]

1,372 g (11.615 mol) of SA, 1,070 g (11.618 mol) of BD, 180.13 g (2.902 mol) of EG and 6.39 g (0.033 mol) of TMA were fed into a reactor equipped with a stirrer and a condenser. Over 120 minutes, and the temperature was raised to 210 DEG C over 120 minutes with stirring. At this time, water, which is produced as a byproduct, was completely drained through a condenser, resulting in 2,356 g of an esterification product. Subsequently, 20 g of the silicone compound S-2 having a viscosity of 1,000 cs and 1.70 g of TBT as a catalyst were introduced, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and while the temperature in the tube was raised to 245 캜, After the reaction was completed, stirring was stopped and nitrogen was poured into the glass to pressurize and discharge the polymer to obtain the desired aliphatic copolymerized polyester. The obtained resin was used for blown film production by hot air drying. The production of the film was carried out by using a "RHEOCORD 90" blown film processing equipment of HAAKE having a hollow die diameter of 25 mm, BLOW-UP RATIO = 4, TAKE-UP A film having a thickness of about 30 탆 was obtained with SPFFD = 20 mm / min, SCREW SPEED = 9 gm, and barrel temperature conditions of 140 캜, 150 캜, 150 캜 and 1507. The tensile strength, The physical properties of the resin were evaluated and shown in Table 3.

[Comparative Example 7]

The procedure of Example 2 was repeated except that 26.9 g (0.139 mol) of TMA was used in the esterification reaction. The results are shown in Table 3.

[Comparative Example 8]

The procedure of Example 2 was repeated except that 130 g of the silicone compound S-2 was used in the condensation polymerization reaction, and the results are shown in Table 3.

[Example 3]

In a reactor equipped with a stirrer and a condenser, SA 1,3729 (11.615 mol), EG 793 g (12.776 mol), BD 208 g (2.258 mol) and TME 6.39 g (0.033 mol) And the temperature was raised to 210 DEG C over 120 minutes while stirring. At this time, the produced water as a byproduct was completely drained out through a condenser, resulting in 2,318 g of an esterification reaction product. Subsequently, 25 g of the silicone compound S-2 having a viscosity of 1,000 cs and 1.70 g of TBT as a catalyst were introduced, and the pressure in the tube was gradually reduced to 0.57 mmHg over 45 minutes, and the temperature was elevated to 24 캜 for 120 minutes After the stirring reaction, the stirring was stopped, and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain the desired aliphatic copolymerized polyester. The obtained resin was used for the production of blown film through hot air drying. The film was produced by using the "RHEOCORD 90" blown film processing equipment of HAAKE, which has a hollow die direct connection of 25 mm, BLOW-VP RATIO = 4, TAKE- A film having a thickness of about 30 탆 was obtained at SPFFD = 20 mm / min, SCREW SPEED = 9 gm, and barrel temperature conditions of 140 캜, 150 캜, 150 캜 and 157 캜. The physical properties of the resulting resin were evaluated and are shown in Table 3.

[Example 4]

1,372 g (11.615 mol) of SA, 1,070 g (11.618 mol) of BD, 302.29 g (2.902 mol) of NPG and 6.39 g (0.033 mol) of TME were charged into a reactor equipped with a stirrer and a condenser. And the temperature was raised to 210 DEG C over 120 minutes while stirring. At this time, water as a byproduct of the reaction was completely drained out through the condenser, resulting in 2,496 g of esterification reaction product. Subsequently, 30 g of the silicone compound S-2 having a viscosity of 1000 cs and 1.70 g of TBT as a catalyst were introduced, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes. While the temperature in the tube was raised to 245 캜, The stirring was stopped and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain the desired aliphatic copolymerized polyester. The obtained resin was used for the production of a blown film through hot air drying. The production of the film was carried out by using a "RHEOCORB 90" blown film processing equipment of a HAAKE company having a hollow die diameter of 25 mm, BLOW-UP RATIO = 4, TAKE- A film having a thickness of about 30 탆 was obtained at SPFFD = 20 mm / min, SCREW SPEED = 9 gm and barrel temperature conditions of 140 캜, 150 캜, 150 캜 and 150 캜. The physical properties of the resulting resin were evaluated and are shown in Table 3.

[Comparative Example 9]

The procedure of Example 4 was repeated except that 26.9 g (0.139 mol) of TMA was used in the esterification reaction. The results are shown in Table 3.

[Comparative Example 10]

The procedure of Example 4 was repeated except that 160 g of silicone compound S-2 was used in the condensation polymerization reaction. The results are shown in Table 3.

[Example 5]

1,372 g (11.615 moles) of SA, 1,070 g (11.618 moles) of BD, 424.17 g (2.902 moles) of CHDM and 6.39 g (0.033 mole) of TME were fed into a reactor equipped with a stirrer and a condenser, And the temperature was raised to 210 DEG C over 120 minutes while stirring. At this time, the generated water as a byproduct was completely drained out through a condenser, resulting in 2,458 g of esterification reaction product. Subsequently, 27 g of the silicone compound S-1 having a viscosity of 1000 cs and 1.70 g of TBT as a catalyst were introduced, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, while stirring was continued for 120 minutes while raising the temperature in the tube to 245 ° C The stirring was stopped and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain a target aliphatic copolymerized polyester. The obtained resin was used for blown film production by hot air drying. The production of the film was carried out by using a "RHEOCORD 90" blown film processing equipment of HAAKE having a hollow die diameter of 25 mm, BLOW-UP RATIO = 4, TAKE-UP SPFFD = 20 mm / min SCREW SPEED = 9 rpm, and barrel temperature conditions of 140 캜, 150 캜, 150 캜 and 150 캜 were obtained. The tensile strength and the HAZE measurement result of the film and the obtained resin The properties are shown in Table 3.

[Table 3] Degradability and Mechanical Properties DATA

Claims (8)

An acid component consisting of succinic acid or a water to be esterified thereof, and 70 to 95 mol% of one component selected from 1,4-butanediol and ethylene glycol, the remainder including 1,6-hexanediol, 2,2- Dimethyl-1,3-propanediol, and 1,6-cyclohexanedimethanol, and a compound having a polyfunctional compound having three or more hydroxyl groups or alcohol groups in a proportion of from 5 to 30 mol% Esterification reaction, and then the organosilicon compound represented by the following general formula (I) is added together with other additives to effect polycondensation. The method of claim 1, wherein the reaction molar ratio of the acid component to the diol component is in the range of 1: 1 to 1: 2. The method for producing an aliphatic copolymer polyester according to claim 1, wherein the polyfunctional compound is used in an amount of 0.01 to 1 mol% based on the acid component. The method of claim 1, wherein the viscosity of the organosilicon compound is in the range of 50 to 50,000 cps. The method of claim 1, wherein the organosilicon compound is used in an amount of 0.1 to 5 wt% based on the ester reactant. The polyfunctional compound according to claim 1, wherein the polyfunctional compound is selected from trimethylol propane, trimethylol ethane, pentaerythritol, dipentaerythritol, trimellitic acid, anhydride, benzene tetracarboxylic acid and benzene tetracarboxylic anhydride Wherein the aliphatic copolymerized polyester is produced by a method comprising the steps of: The method for producing an aliphatic copolymerized polyester according to any one of claims 1 to 6, wherein the polycondensation reaction is carried out at a temperature in the range of 240 to 260 캜. An acid component consisting of succinic acid or its ester compound and 70 to 95 mol% of one component selected from 1,4-butanediol and ethylene glycol, 1,6-hexanediol, 2,2-dimethyl- 1,3-propanediol and 1,6-cyclohexanedimethanol, and a polyfunctional compound having three or more hydroxyl groups or alcohol groups, in an esterification reaction And then adding the organosilicon compound of the general formula (I) together with other additives to polycondensate the aliphatic polyester copolymer by melt extrusion and stretching in an up and down direction through a circular hollow die. Esterblown film. ※ Note: It is disclosed by the contents of the first application.