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WO2010103884A1 - Composition de résine polyglycolique et objet moulé constitué de celle-ci - Google Patents

Composition de résine polyglycolique et objet moulé constitué de celle-ci Download PDF

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Publication number
WO2010103884A1
WO2010103884A1 PCT/JP2010/051871 JP2010051871W WO2010103884A1 WO 2010103884 A1 WO2010103884 A1 WO 2010103884A1 JP 2010051871 W JP2010051871 W JP 2010051871W WO 2010103884 A1 WO2010103884 A1 WO 2010103884A1
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Prior art keywords
resin composition
polyglycolic acid
compound
acid resin
pga
Prior art date
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Ceased
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PCT/JP2010/051871
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English (en)
Japanese (ja)
Inventor
浩幸 佐藤
文夫 阿久津
史典 小林
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Kureha Corp
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Kureha Corp
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Publication of WO2010103884A1 publication Critical patent/WO2010103884A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a polyglycolic acid resin composition, and more particularly to a polyglycolic resin composition that is excellent in water resistance and hardly undergoes coloration due to heat.
  • Polyglycolic acid-based resins are attracting attention as biodegradable polymer materials with a low environmental impact because they are excellent in microbial degradability and hydrolyzability.
  • this polyglycolic acid resin is heated for a long time at the time of melt kneading or melt molding, there is a problem that it is depolymerized by heat to generate glycolide and hydrolyze, or decomposes and colors by heat. . Therefore, in order to improve water resistance (hydrolysis resistance) and heat resistance (thermal stability), a heat stabilizer, an antioxidant and the like have been conventionally added to the polyglycolic acid resin.
  • Patent Document 1 discloses a phosphorus compound having at least one hydroxyl group and at least one long-chain alkyl ester group represented by mono- or distearyl acid phosphate in polyglycolic acid. It is disclosed that the melt stability of polyglycolic acid is improved by adding a heat stabilizer such as.
  • Patent Document 2 discloses a long-chain alkyl ester of (sub-) phosphoric acid having a specific basicity such as monostearyl phosphate or distearyl phosphate in an aliphatic polyester resin. It is disclosed that the water resistance (hydrolysis resistance) of the aliphatic polyester resin composition is improved by adding a carboxylic acid, and further by adding a carboxyl group sealing agent such as a carbodiimide compound. It is also disclosed that the improvement is further improved.
  • Patent Document 3 includes a polyglycolic acid resin and a long-chain alkyl ester of (sub-) phosphoric acid represented by an approximately equimolar mixture of mono- and distearyl acid phosphates. It is disclosed that the water resistance and thermal stability of a molded product obtained from the polyglycolic acid resin composition are improved by adding a carboxyl group-capping agent such as a heat stabilizer and / or a carbodiimide compound. .
  • a carboxyl group-capping agent such as a heat stabilizer and / or a carbodiimide compound.
  • JP-A-2007-126653 discloses at least one hydroxyl group represented by a mixture of about 50 mol% monostearyl phosphate and about 50 mol% distearyl phosphate in an aliphatic polyester resin.
  • the heat resistance of the aliphatic polyester resin composition is obtained by sequentially heating and melting and mixing a heat stabilizer such as an alkyl phosphite having at least one alkyl ester group and a carboxyl group sealing agent such as a carbodiimide compound. It is disclosed that coloration by heat and heat is improved.
  • Patent Document 5 JP 2007-23082 A (Patent Document 5) improves the hydrolysis resistance and stretchability of a polyglycolic acid resin composition by adding a predetermined amount of a phenolic resin to the polyglycolic acid resin.
  • Thermal stabilizers such as phosphoric acid or alkyl esters of phosphorous acid are also disclosed.
  • Patent Document 6 discloses a composition containing an aliphatic polyester, an antioxidant and an anti-coloring agent as an aliphatic polyester composition with little coloring.
  • Phosphorus processing stabilizers such as hindered phenolic antioxidants and triphenyl phosphite are disclosed as inhibitors, and trialkyl phosphates typified by tributyl phosphate are disclosed as coloring inhibitors.
  • JP-A-2003-313436 Patent Document 7) discloses biodegradable plastics, carbodiimide compounds, and antioxidants as biodegradable plastic compositions that improve hydrolysis resistance and heat resistance and retain transparency.
  • a composition containing an agent is disclosed.
  • Patent Document 7 discloses a mixture of a hindered phenolic antioxidant and a phosphite antioxidant as a preferred antioxidant.
  • Patent Document 8 describes hydrolysis inhibition of polyester resins, carbodiimide compounds, etc. as a polyester resin composition that has hydrolysis resistance and preserves resin properties over a long period of time.
  • a polyester resin composition containing an agent, a phosphorus stabilizer and a phenol stabilizer is disclosed.
  • Phosphoric esters such as trioctyl phosphate and triphenyl phosphate are used as phosphorus stabilizers, and hinders are used as phenol stabilizers. Dophenol stabilizers are disclosed.
  • the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a polyglycolic acid resin composition that is excellent in water resistance and hardly colored by heat.
  • the present inventors only improved the water resistance by adding a hindered phenol compound and an acid phosphate compound to the polyglycolic acid resin.
  • the present inventors have found that coloring due to heat is suppressed and completed the present invention.
  • the polyglycolic acid resin composition of the present invention contains a polyglycolic acid resin, a hindered phenol compound, and an acid phosphate compound.
  • R represents a hydrocarbon group having 7 to 24 carbon atoms, and when a plurality of R are present, they may be the same or different, and m is 1 or 2. is there.
  • a compound in which R in the formula (1) is an alkyl group having 7 to 24 carbon atoms is more preferable.
  • the content of the acid phosphate compound is preferably 0.003 to 3 parts by mass with respect to 100 parts by mass of the polyglycolic acid resin.
  • the hindered phenol compound is preferably a compound in which a tert-butyl group is introduced into at least one carbon atom of the ortho position of the phenol skeleton.
  • the content of the hindered phenol compound in terms of phenolic hydroxyl group is preferably 0.3 to 30 ⁇ mol with respect to 1 g of the polyglycolic acid resin.
  • the molded article of the present invention is obtained from the polyglycolic acid resin composition of the present invention.
  • the water resistance of the polyglycolic acid resin composition is improved by using a hindered phenol compound and an acid phosphate compound together as in the present invention, and the reason why coloring due to heat is further suppressed is not always clear.
  • the present inventors speculate as follows. That is, the catalyst used in the synthesis of the polyglycolic acid resin usually remains in the polyglycolic acid resin composition. When such a polyglycolic acid resin composition is heated, the polyglycolic acid resin is not only directly depolymerized and decomposed by heat, but also due to the action of the catalyst under heating, Depolymerize or decompose. When such depolymerization occurs, glycolide is generated, so that the water resistance of the composition is lowered, and when the decomposition occurs, the composition is colored.
  • the polyglycolic acid resin composition of the present invention since a hindered phenol compound and an acid phosphate compound exist, they interact with each other to directly depolymerize or thermally decompose as described above. In addition, it is presumed that depolymerization and decomposition due to catalytic action under heating are also suppressed, water resistance is improved, and coloring is less likely to occur. In particular, it is presumed that the acid phosphate compound suppresses depolymerization and decomposition due to catalytic action under heating by forming a chelate with the catalyst.
  • the polyglycolic acid resin composition (hereinafter referred to as “PGA resin composition”) of the present invention comprises a polyglycolic acid resin (hereinafter referred to as “PGA resin”), a hindered phenol compound, and acid phosphate. Containing a fate compound.
  • PGA resin composition comprises a polyglycolic acid resin (hereinafter referred to as “PGA resin”), a hindered phenol compound, and acid phosphate. Containing a fate compound.
  • PGA resin As the PGA-based resin used in the present invention, the following formula (1): — [O—CH 2 —C ( ⁇ O)] — (1)
  • a glycolic acid homopolymer consisting only of glycolic acid repeating units represented by the formula hereinafter referred to as “PGA homopolymer”, including a ring-opened polymer of glycolide which is a bimolecular cyclic ester of glycolic acid).
  • PGA copolymer a polyglycolic acid copolymer containing glycolic acid repeating units
  • Such PGA-type resin may be used individually by 1 type, or may use 2 or more types together. From the viewpoint of heat resistance, gas barrier properties, and mechanical strength, the PGA resin is preferably crystalline.
  • the comonomers used together with the glycolic acid monomer in producing the PGA copolymer include ethylene oxalate (ie, 1,4-dioxane-2,3-dione), lactides, lactones (for example, ⁇ -Propiolactone, ⁇ -butyrolactone, ⁇ -pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, etc.), carbonates (eg trimethylene carbonate, etc.), ethers (For example, 1,3-dioxane, etc.), cyclic monomers such as ether esters (eg, dioxanone), amides ( ⁇ -caprolactam, etc.); lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4- Hydro, such as hydroxybutanoic acid and 6-hydroxycaproic acid Cicarboxylic acids or alkyl esters
  • the catalyst used when the PGA resin is produced by ring-opening polymerization of glycolide includes tin compounds such as tin halide and tin organic carboxylate; titanium compounds such as alkoxy titanate; aluminum such as alkoxyaluminum.
  • Known ring-opening polymerization catalysts such as zirconium compounds, zirconium compounds such as zirconium acetylacetone, and antimony compounds such as antimony halide and antimony oxide.
  • the PGA-based resin can be produced by a conventionally known polymerization method.
  • the polymerization temperature is preferably 120 to 300 ° C., more preferably 130 to 250 ° C., particularly preferably 140 to 220 ° C., and 150 to 200. C is most preferred.
  • the polymerization temperature is less than the lower limit, the polymerization tends not to proceed sufficiently.
  • the polymerization temperature exceeds the upper limit, the produced resin tends to be thermally decomposed.
  • the polymerization time for the PGA resin is preferably 2 minutes to 50 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 18 hours.
  • the polymerization time is less than the lower limit, the polymerization does not proceed sufficiently, whereas when the upper limit is exceeded, the generated resin tends to be colored.
  • the content of the glycolic acid repeating unit represented by the formula (1) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. 100 mass% is particularly preferable.
  • the content of the glycolic acid repeating unit is less than the lower limit, heat resistance and gas barrier properties tend to decrease.
  • the weight average molecular weight of the PGA resin is preferably 30,000 to 800,000, more preferably 50,000 to 500,000.
  • the weight average molecular weight of the PGA-based resin is less than the lower limit, the mechanical strength of the PGA-based resin molded product tends to be lowered. On the other hand, when it exceeds the upper limit, melt extrusion and molding tend to be difficult.
  • the weight average molecular weight is a polymethylmethacrylate conversion value measured by gel permeation chromatography (GPC).
  • the melt viscosity (temperature: 240 ° C., shear rate: 100 sec ⁇ 1 ) of the PGA-based resin is preferably 100 to 10,000 Pa ⁇ s, more preferably 300 to 8000 Pa ⁇ s, and particularly preferably 400 to 5000 Pa ⁇ s. .
  • the melt viscosity is less than the lower limit, the mechanical strength of the PGA-based resin composition tends to decrease.
  • melt viscosity exceeds the upper limit, melt extrusion or molding tends to be difficult.
  • the hindered phenol compound is a phenol compound in which a substituent is introduced into carbon atoms at both ortho positions of the phenol skeleton, and at least one of them is a substituent capable of becoming a steric hindrance.
  • the substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the substituent that can cause steric hindrance include a bulky alkyl group such as a butyl group. A butyl group is preferred.
  • the substituent which may become a steric hindrance is introduced into carbon atoms at both ortho positions.
  • Such hindered phenol compounds include tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, 4,4′-methylene-bis (2,6-di-tert-butylphenol), pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-to Such as methyl-2,4,6-tris (3,5-di -tert- buty
  • the content of the hindered phenol compound is preferably 0.3 to 30 ⁇ mol, more preferably 0.5 to 10 ⁇ mol, in terms of phenolic hydroxyl group, with respect to 1 g of PGA resin. 0.7 to 3 ⁇ mol is particularly preferable.
  • the content of the hindered phenol compound is less than the lower limit, the PGA resin composition tends to be colored.
  • the content exceeds the upper limit the melt viscosity of the PGA resin composition is lowered, and the mechanical strength is decreased. It tends to decrease.
  • the compound represented by these is mentioned.
  • the acid phosphate compound forms a chelate with the polymerization catalyst used in the synthesis of the PGA resin and suppresses the catalytic action of the polymerization catalyst, whereby the PGA due to the catalytic action under heating is used. It is presumed that depolymerization and decomposition of the resin are suppressed.
  • R in the formula (1) represents a hydrocarbon group having 7 to 24 carbon atoms (preferably 8 to 20 carbon atoms), preferably an alkyl group having 7 to 20 carbon atoms (more preferably 8 to 20 carbon atoms). Represents. m is 1 or 2. When a plurality of Rs in the formula (1) are present, they may be the same or different groups.
  • acid phosphate compounds include mono (2-ethylhexyl) acid phosphate, monoisodecyl acid phosphate, monostearyl acid phosphate, monoalkyl acid phosphate such as monolauryl acid phosphate; monophenyl acid phosphate Monoaryl phosphates represented by: di (2-ethylhexyl) acid phosphates, diisodecyl acid phosphates, distearyl acid phosphates, dialkyl acid phosphates such as dilauryl acid phosphates; diaryls represented by diphenyl acid phosphates For example, phosphate.
  • monostearyl acid phosphate and distearyl acid phosphate are preferable from the viewpoint of thermal stability at the melt kneading temperature.
  • these acid phosphate compounds may be used individually by 1 type, or may use 2 or more types together.
  • the content of the acid phosphate compound in the PGA resin composition of the present invention is preferably 0.003 to 3 parts by mass, more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the PGA resin. 0.01 to 0.5 parts by mass is particularly preferable.
  • the content of the acid phosphate compound is less than the lower limit, depolymerization and decomposition due to catalytic action are not sufficiently suppressed, and glycolide tends to increase.
  • the content exceeds the upper limit the melt viscosity of the PGA resin composition is increased. Tends to decrease and the mechanical strength tends to decrease.
  • various additives such as a heat stabilizer, a terminal blocking agent, a plasticizer, a heat ray absorber, and an ultraviolet absorber, and other thermoplastics, as long as the effects of the present invention are not impaired.
  • Resin can be added.
  • the PGA resin composition of the present invention contains the PGA resin, the hindered phenol compound, and the acid phosphate compound, and depolymerization of the PGA resin hardly occurs even under heating. Since the production of glycolide is suppressed, the water resistance is excellent. In addition, the PGA-based resin is not easily decomposed and is not easily colored during melt kneading. Furthermore, even if such a PGA-based resin composition is molded by a molding process involving heating such as an extrusion molding process, a molded body in which coloring is suppressed is obtained.
  • Such a PGA resin composition of the present invention can be produced by mixing the PGA resin, the hindered phenol compound, the acid phosphate compound, and other additives as necessary. it can. At this time, melt kneading is preferably performed using an extruder or the like. Thereby, it becomes possible to fully express the addition effect of additives, such as a hindered phenol type compound and an acid phosphate compound.
  • the temperature at the time of melt kneading is preferably 200 to 300 ° C., more preferably 230 to 280 ° C., and particularly preferably 240 to 270 ° C.
  • the melt kneading temperature is less than the lower limit, the effect of adding additives such as hindered phenolic compounds and acid phosphate compounds tends not to be sufficiently exhibited.
  • the upper limit is exceeded, the PGA resin composition is colored. It tends to be easy.
  • a stirrer or a continuous kneader can be used in addition to the extruder, but an extruder (from the viewpoint that a short time treatment is possible and a smooth transition to the subsequent cooling step is possible.
  • an extruder from the viewpoint that a short time treatment is possible and a smooth transition to the subsequent cooling step is possible.
  • a method using a twin screw kneading extruder is preferable.
  • glycolide is subjected to ring-opening polymerization to synthesize a partial polymer.
  • solid pulverized product of this partial polymer is subjected to solid phase polymerization, and the resulting polymer is subjected to the hindered phenolic compound and the above-mentioned polymer.
  • a method in which an additive such as an acid phosphate compound is added and melt-kneaded is preferred.
  • the yellowness (YI) of this molded product was measured by a reflected light measurement method using a spectrocolorimeter (“TC-1800” manufactured by Tokyo Denshoku Co., Ltd.) under the conditions of standard light C, 2 degree visual field and color system. It was measured.
  • a reactor comprising a main body provided with a jacket-structure reaction tube (made of SUS304, inner diameter 24 mm) and two jacket-structure metal plates (made of SUS304) was prepared.
  • a jacket-structure reaction tube made of SUS304, inner diameter 24 mm
  • two jacket-structure metal plates made of SUS304
  • the temperature of the liquid mixture is maintained at 100 ° C. from the upper opening of the reaction tube. It was transferred as it was.
  • the other metal plate hereinafter referred to as “upper plate” was attached and the reaction tube was sealed. Thereafter, a heat medium oil at 170 ° C. was circulated through the main body and a jacket of two metal plates and held for 7 hours to synthesize a polyglycolic acid resin (PGA resin).
  • PGA resin polyglycolic acid resin
  • the obtained PGA resin block was pulverized by a pulverizer.
  • the weight average molecular weight (in terms of polymethyl methacrylate) in the GPC measurement of the obtained PGA resin was 225000.
  • Example 1 In 100 parts by mass of the PGA resin obtained in the above synthesis example, 0.030 parts by mass of a substantially equimolar mixture of mono- and distearyl acid phosphates (“ADEKA STAB AX-71” manufactured by ADEKA) and a hinder 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (“ADEKA STAB AO-330” manufactured by ADEKA Corporation) as a dophenol compound 0.030 part by mass was added.
  • ADEKA STAB AX-71 substantially equimolar mixture of mono- and distearyl acid phosphates
  • ADEKA STAB AO-330 manufactured by ADEKA Corporation
  • a twin-screw kneading extruder (“LT” manufactured by Toyo Seiki Seisakusho Co., Ltd.) in which the temperature of four sections provided between the supply section and the discharge section was set to 220 ° C., 230 ° C., 250 ° C., and 230 ° C. in this order. -20 ") and melt-kneading extrusion was performed to obtain a pellet-like PGA resin composition.
  • Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 2 A pellet-like PGA resin composition was obtained in the same manner as in Example 1 except that 0.030 parts by mass of diisodecyl acid phosphate (“DP-10R” manufactured by Daihachi Chemical Co., Ltd.) was added as the acid phosphate compound. .
  • Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 3 Pellet PGA as in Example 1 except that 0.017 parts by mass of bis (2-ethylhexyl) acid phosphate (“DP-8R” manufactured by Daihachi Chemical Industry Co., Ltd.) was added as the acid phosphate compound. A resin composition was obtained. Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • DP-8R bis (2-ethylhexyl) acid phosphate
  • Example 4 Addition of 0.050 parts by mass of n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (“ADEKA STAB AO-50” manufactured by ADEKA Corporation) as a hindered phenol compound
  • ADEKA STAB AO-50 manufactured by ADEKA Corporation
  • Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 5 Add 0.050 parts by mass of triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (“Irganox245” manufactured by Ciba Japan Co., Ltd.) as a hindered phenol compound
  • Irganox245 triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate]
  • Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 6 The amount of hindered phenolic compound 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene added was changed to 0.010 parts by mass.
  • a pellet-like PGA resin composition was obtained in the same manner as in Example 1 except that. Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 1 A pellet-like PGA resin composition was obtained in the same manner as in Example 1 except that the hindered phenol compound was not added. Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 2 A pellet-like PGA resin composition was obtained in the same manner as in Example 1 except that the acid phosphate compound was not added. Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 4 A pellet-like PGA resin composition was obtained in the same manner as in Example 1 except that 0.030 parts by mass of tributyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added instead of the acid phosphate compound.
  • Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • Example 5 A pellet-like PGA resin composition was obtained in the same manner as in Example 1 except that 0.030 parts by mass of triphenyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added instead of the acid phosphate compound.
  • Table 1 shows the measurement results of the glycolide content of this PGA resin composition and the results of the thermal stability test.
  • the PGA resin composition was a glycol. It was confirmed that the content was low and the water resistance was excellent, and that coloring due to heat was small.
  • the PGA resin composition had a low glycol content and was excellent in water resistance, but was colored by heat.
  • the PGA resin composition in the case where no acid phosphate compound was added (Comparative Example 2) and in the case where a phosphite compound, trialkyl phosphate or triphenyl phosphate was added (Comparative Examples 3 to 5), the PGA resin composition was colored by heat and had a high glycol content and poor water resistance.
  • the water resistance of the PGA resin composition is improved, and further, coloring due to heat can be suppressed. It becomes.
  • the water resistance of the PGA-based resin composition can be improved without adding a water resistance improver such as a carboxyl group blocking agent.
  • the film is produced by a molding method involving heating or melting, such as stretch molding, extrusion molding, or injection molding. It is useful as a raw material for sheets, sheets, fibers, containers, and the like, and is particularly useful as a raw material for those requiring colorless transparency.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne une composition de résine polyglycolique caractérisée en ce qu'elle comprend une résine d'acide polyglycolique, un composé phénol encombré et un composé phosphate acide, et un objet moulé constitué de la composition de résine.
PCT/JP2010/051871 2009-03-12 2010-02-09 Composition de résine polyglycolique et objet moulé constitué de celle-ci Ceased WO2010103884A1 (fr)

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JP2009059917A JP5406569B2 (ja) 2009-03-12 2009-03-12 ポリグリコール酸系樹脂組成物およびその成形体

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2018139107A1 (ja) * 2017-01-24 2019-11-07 株式会社クレハ α−ヒドロキシカルボン酸２量体環状エステルの製造方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013139496A (ja) * 2011-12-28 2013-07-18 Kureha Corp ポリグリコール酸系樹脂組成物およびその製造方法、並びにそれを用いた延伸成形用積層体および延伸積層体
JP2015155587A (ja) * 2013-11-05 2015-08-27 三菱化学株式会社 脂肪族ポリエステル樹脂繊維及び脂肪族ポリエステル樹脂組成物
US20180045215A1 (en) * 2015-03-25 2018-02-15 Mitsubishi Heavy Industries, Ltd. Impeller for rotary machine, compressor, supercharger, and method for producing impeller for rotary machine

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003037956A1 (fr) * 2001-10-31 2003-05-08 Kureha Chemical Industry Company, Limited Acide polyglycolique cristallin, composition a base d'acide polyglycolique et procedes de fabrication correspondants
JP2004231953A (ja) * 2003-01-10 2004-08-19 Mitsui Chemicals Inc ポリエステル樹脂組成物
WO2007034805A1 (fr) * 2005-09-21 2007-03-29 Kureha Corporation Procédé de production d’une composition de résine de poly(acide glycolique)
JP2008248138A (ja) * 2007-03-30 2008-10-16 Mitsubishi Chemicals Corp 低温特性に優れた樹脂組成物の成型体
JP2008266572A (ja) * 2007-01-17 2008-11-06 Mitsubishi Chemicals Corp 樹脂組成物及びその製造方法、並びに共重合体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003037956A1 (fr) * 2001-10-31 2003-05-08 Kureha Chemical Industry Company, Limited Acide polyglycolique cristallin, composition a base d'acide polyglycolique et procedes de fabrication correspondants
JP2004231953A (ja) * 2003-01-10 2004-08-19 Mitsui Chemicals Inc ポリエステル樹脂組成物
WO2007034805A1 (fr) * 2005-09-21 2007-03-29 Kureha Corporation Procédé de production d’une composition de résine de poly(acide glycolique)
JP2008266572A (ja) * 2007-01-17 2008-11-06 Mitsubishi Chemicals Corp 樹脂組成物及びその製造方法、並びに共重合体
JP2008248138A (ja) * 2007-03-30 2008-10-16 Mitsubishi Chemicals Corp 低温特性に優れた樹脂組成物の成型体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2018139107A1 (ja) * 2017-01-24 2019-11-07 株式会社クレハ α−ヒドロキシカルボン酸２量体環状エステルの製造方法
US11046665B2 (en) 2017-01-24 2021-06-29 Kureha Corporation Method for producing α-hydroxycarboxylic acid dimeric cyclic ester

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