WO2012046709A1 - 生分解性樹脂組成物 - Google Patents
生分解性樹脂組成物 Download PDFInfo
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- WO2012046709A1 WO2012046709A1 PCT/JP2011/072819 JP2011072819W WO2012046709A1 WO 2012046709 A1 WO2012046709 A1 WO 2012046709A1 JP 2011072819 W JP2011072819 W JP 2011072819W WO 2012046709 A1 WO2012046709 A1 WO 2012046709A1
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- biodegradable resin
- resin composition
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- polyglycolic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- the present invention relates to a biodegradable resin composition containing, as a main component, a hardly hydrolyzable biodegradable resin such as polylactic acid. More specifically, the degradability of the biodegradable resin is enhanced.
- the present invention relates to a biodegradable resin composition and a molded body formed from the biodegradable resin.
- Patent Document 1 proposes a lactic acid resin composition containing polylactic acid as a main component and a molded product thereof.
- a molded body made of a biodegradable resin such as polylactic acid is hardly hydrolyzable, so it takes time to decompose due to the action of an enzyme.
- a molded body such as a container the surface of the molded body is affected by the action of the enzyme. Since the decomposition proceeds, it takes a long time until the biodegradable resin forming the molded body is completely decomposed, and the property of biodegradability is not fully utilized.
- a biodegradable resin composition in which an aliphatic polyester such as polyethylene oxalate is blended as an ester decomposition accelerator in a biodegradable resin such as polylactic acid.
- Aliphatic polyesters such as polyethylene oxalate blended in this biodegradable resin composition are easily hydrolysable and easily hydrolyze to release acid when mixed with water. It functions as an agent. That is, since the released acid accelerates the hydrolysis of the biodegradable resin, the degradation of the biodegradable resin by the enzyme can be significantly accelerated.
- Patent Document 3 proposes a resin composition containing a biodegradable resin and alkali-release particles.
- the alkali sustained-release particles have a shell core structure containing an alkaline substance as a core and a porous substance as a shell, and the alkali sustained-release particles also function as an ester decomposition accelerator.
- an alkaline substance is eluted from the alkali sustained release particles, thereby promoting hydrolysis of the biodegradable resin and promoting degradation of the biodegradable resin by the enzyme. It is said that.
- biodegradable resin composition containing an aliphatic polyester that functions as an ester decomposition accelerator or an alkali sustained release particle, acid or alkali is gradually released from the decomposition accelerator when it comes into contact with moisture.
- the biodegradability of the biodegradable resin is accelerated compared to the case where such an ester decomposition accelerator is not blended, but the degree is not sufficient, and the biodegradability is further improved. It is demanded to make it.
- an object of the present invention is to provide a biodegradable resin composition capable of rapidly degrading a biodegradable resin and a molded body molded from the biodegradable resin composition.
- the present invention includes a hardly hydrolyzable biodegradable resin (A), a polyglycolic acid (B), and an ester decomposition accelerating aid (C) comprising inorganic particles that promote hydrolysis of the polyglycolic acid.
- a biodegradable resin composition is provided.
- molded using the said biodegradable resin composition is provided.
- the inorganic particles are basic compounds containing an alkali metal or an alkaline earth metal, (2) the basic compound is calcium carbonate and / or sodium carbonate; (3)
- the polyglycolic acid (B) is contained in an amount of 0.01 to 30 parts by weight per 100 parts by weight of the biodegradable resin (A), and the ester decomposition promoting aid (C) It is contained in an amount of 28 to 200 parts by weight per 100 parts by weight of glycolic acid (B). Is preferred.
- the polyglycolic acid (B) is hydrolyzed by contact with moisture to release an acid that can act as an ester decomposition catalyst.
- inorganic particles for example, calcium carbonate
- ester decomposition accelerating aids C. It is blended as That is, since polyglycolic acid (B) is a polymer and hydrolyzes in contact with moisture, the hydrolysis is an organic reaction, and the reaction rate is significantly slower than that of a normal inorganic reaction.
- the hydrolysis rate of polyglycolic acid (B) is slow, and the hydrolysis of the biodegradable resin is accelerated by the released acid. It will take a considerable amount of time (ie, the initial rate of degradation of the biodegradable resin is slow).
- the hydrolysis (acid release) of the polyglycolic acid (B) is promoted by blending the inorganic particles as described above as the ester decomposition accelerating aid (C).
- ester decomposition accelerating aid has a function of accelerating the hydrolysis of the hardly hydrolyzable biodegradable resin itself.
- the hydrolysis promoting function by the polyglycolic acid (B) can be exhibited in a short time (the initial rate of degradation of the biodegradable resin is increased), and the ester degradation promoting aid (C). Hydrolysis of the biodegradable resin is also promoted, and the biodegradation rate can be remarkably improved.
- the present invention it is possible to quickly disintegrate a molded body formed from this biodegradable resin composition, which is extremely advantageous in avoiding environmental destruction such as an increase in dust and the like.
- the molded body can be collected, and the biodegradable resin can be reused and recycled.
- the biodegradable resin composition of the present invention contains a hardly hydrolyzable biodegradable resin (A) as a main component, and further contains a polyglycolic acid (B) and an ester decomposition accelerating aid (C).
- A hardly hydrolyzable biodegradable resin
- B polyglycolic acid
- C ester decomposition accelerating aid
- the biodegradable resin used is hardly hydrolyzable.
- an aqueous dispersion having a concentration of 10 mg / 10 ml is prepared from a sample obtained by freeze-pulverizing and pulverizing the biodegradable resin. This refers to a TOC (total organic carbon content) of 5 ppm or less after incubation for 1 week at 0 ° C.
- water-soluble polyester is not included.
- examples of such hardly hydrolyzable biodegradable resins include polylactic acid, polyhydroxyalkanoate, polycaprolactone, polybutylene succinate, cellulose acetate and the like, which are copolymers and blends. It can also be used in the form of objects.
- the polylactic acid may be either 100% poly-L-lactic acid or 100% poly-D-lactic acid, or a melt blend of poly-L-lactic acid and poly-D-lactic acid. It may be a random copolymer or block copolymer of L-lactic acid and D-lactic acid.
- the above-mentioned biodegradable resin (A) is copolymerized with various aliphatic polyhydric alcohols, aliphatic polybasic acids, hydroxycarboxylic acids, lactones, etc., as long as the characteristics of the biodegradable resin are not impaired. It can also be used in the form of a copolymer.
- polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, octanediol, dodecanediol, neopentyl glycol, glycerin, pentaerythritol, sorbitan, and polyethylene glycol.
- Examples of the polybasic acid include oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, and terephthalic acid.
- Examples of the hydroxycarboxylic acid include glycolic acid, hydroxypropionic acid, hydroxyvaleric acid, hydroxycaproic acid, and mandelic acid.
- Examples of the lactone include caprolactone, butyrolactone, valerolactone, poropiolactone, undecalactone, glycolide, and mandelide.
- the biodegradable resin (A) described above should have a molecular weight sufficient to form a film from the viewpoint of moldability, and generally has a weight average molecular weight of 5,000 to 1,000,000. In particular, it should be in the range of 10,000 to 500,000.
- polylactic acid is optimal from the viewpoint of being suitably applied in the field of packaging materials such as containers.
- biodegradable resin (A) is hardly hydrolyzable and requires a very long time for its decomposition. Therefore, the following polyglycolic acid (B) and ester decomposition accelerating aid (C) are blended. , Improve its degradation rate.
- Polyglycolic acid (B) is an easily hydrolyzable polymer that releases an acid that functions as a catalyst for ester decomposition when mixed with moisture, and is uniformly dispersed throughout the biodegradable resin (A).
- those having a weight average molecular weight of about 1000 to 500,000 are used.
- the polyglycolic acid (B) varies depending on the type thereof, but is generally used in an amount of 0.01 to 30 parts by weight, particularly 1 to 10 parts by weight per 100 parts by weight of the biodegradable resin (A). Is preferred. If the amount of the polyglycolic acid (B) used is too small, it may be difficult to promote the decomposition of the biodegradable resin (A). For example, a polyglycolic acid having a molecular weight of 20,000 or less is more than necessary. This is because if the resin composition is used in a large amount, decomposition of the biodegradable resin may start at the stage of preparing the resin composition or at the stage of use as a molded body.
- the ester decomposition accelerating aid (C) is an inorganic particle used to promote hydrolysis of the polyglycolic acid (B).
- a basic compound containing an alkali metal or an alkaline earth metal, or an alkali metal Typical examples are zeolites that release ions of alkaline earth metals and ion-releasing fillers. That is, such inorganic particles promote hydrolysis of polyglycolic acid (B) during molding and / or in the presence of water.
- Basic compounds containing alkali metals or alkaline earth metals include sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, calcium silicate, magnesium silicate , Sodium phosphate, calcium hydroxide, magnesium hydroxide and the like.
- the ion releasing filler examples include oxide glasses such as aluminosilicate glass, borosilicate glass and sorter lime glass containing alkali metal and alkaline earth metal, and fluoride glass such as zirconium fluoride glass. it can.
- the ester decomposition promoting aid (C) may be used alone or in combination.
- the present invention from the viewpoint of little influence on the environment, no adverse effects on the properties of the biodegradable resin (A), and the decomposition of inorganic particles during thermoforming of the resin composition does not occur.
- the inorganic particles exemplified in the above basic compounds containing calcium and / or sodium, zeolite capable of releasing calcium ions and / or sodium ions, and calcium ion and / or sodium ion releasing fillers are preferable.
- Sodium carbonate is optimal.
- the above-mentioned inorganic particles have an average particle size (average particle size D 50 in terms of volume by laser diffraction scattering method) of 10 ⁇ m or less, particularly 0.01 ⁇ m to from the viewpoint of uniformly dispersing in the resin composition.
- the thing in the range of 5 micrometers is preferable.
- Such inorganic particles are preferably used in an amount of 28 to 200 parts by weight, particularly 30 to 100 parts by weight per 100 parts by weight of the polyglycolic acid (B). If the amount of the inorganic particles is too large, the thermoformability of the resin composition is impaired, or the polyglycolic acid (B) or the biodegradable resin (A) is hydrolyzed in the molded body molded from the resin composition. It may be promoted to cause inconveniences such as damage to the shape of the molded body. If the amount of the inorganic particles is too small, it may be difficult to increase the decomposition rate of the biodegradable resin.
- sodium carbonate has the largest hydrolysis promoting function for polyglycolic acid (B) and biodegradable resin (A). For this reason, when sodium carbonate is used alone. May extremely reduce the molecular weight of the biodegradable resin (A) during thermoforming, and may further reduce the product value due to discoloration of the biodegradable resin (A). Therefore, when using sodium carbonate, the amount is preferably in the range of 0.1 to 35 ppm with respect to the biodegradable resin (A), and is preferably used in combination with calcium carbonate.
- the total blending amount is within the above-mentioned range, that is, 28 to 200 parts by weight, particularly 30 to 100 parts by weight per 100 parts by weight of polyglycolic acid (B). It is better to be in the range of parts.
- the biodegradable resin composition of the present invention can also contain various resin additives in addition to the components described above, for example, in an amount that does not impair the moldability and biodegradability of the biodegradable resin.
- resin additives plasticizers, light stabilizers, antioxidants, UV absorbers, flame retardants, colorants, pigments, fillers, mold release agents, antistatic agents, fragrances, foaming agents, antibacterial / antifungal agents, nucleating materials, etc. It is also possible to blend other thermoplastic resins if necessary.
- the biodegradable resin composition of the present invention containing the various components described above is prepared by mixing the components (A) to (C) described above at the same time so that the components do not decompose (for example, about 150 ° C. to 240 ° C. ) By melt-kneading in an extruder.
- the polyglycolic acid (B) or (C) component ester decomposition promoting aid and the biodegradable resin (A) may be mixed simultaneously, or the polyglycolic acid (B) or (C) component.
- a master batch of each component of the ester decomposition acceleration aid may be prepared and mixed with the biodegradable resin (A).
- the resin composition is used as a molded article having various shapes by a known molding method such as extrusion molding, injection molding, compression molding, and the like, and can be suitably used in the field of packaging materials.
- the above-described biodegradable resin composition can be used as a packaging film or sheet.
- the film can be used as a bag-like container ( Can be used as a pouch).
- the film or sheet can be used as a cup-shaped or tray-shaped container by vacuum forming, pressure forming, stretch forming, plug assist forming, or the like.
- a cup-shaped container or a tray-shaped container may be directly molded by injection molding or compression molding.
- it can be used as a test tube-shaped preform by injection molding or the like, and can be used as a bottle-shaped container by blow molding using this preform.
- a molded body such as a container molded using the biodegradable resin composition of the present invention may be supplied to a decomposition tank as it is upon disposal, but this is appropriately cut into small pieces by cutting, crushing, or the like. After that, it is supplied to the decomposition tank and decomposed.
- This decomposition treatment is performed in an aqueous medium in the presence of a catalyst.
- a catalyst a water-containing solid acid catalyst, for example, activated clay having a high specific surface area obtained by acid treatment of smectite clay such as acid clay or bentonite can be used, but an enzyme is used. Is preferred. That is, not only in terms of environmental impact and waste treatment, but also when an enzyme is used as a catalyst, the hydrolysis of polyglycolic acid (B) from the inside of the molded body due to the penetration of moisture into the molded body. Progresses and the hydrolysis of the biodegradable resin (A) is promoted, and at the same time, the enzyme quickly penetrates into the molded body (waste). This is very advantageous in that the decomposition of A) occurs and the molded product can be decomposed in a short time until it completely disintegrates.
- Examples of the enzyme as described above include protease, cellulase, cutinase, lipase and the like, and these enzymes may be immobilized or not immobilized.
- protease K manufactured by Wako Pure Chemical Industries, Ltd. is used in the form of an aqueous solution.
- microorganisms may be put in and the extracellular enzyme may be used, and the culture medium component and nutrient component which the microorganism requires may be added.
- the solvent during the decomposition treatment as described above can be performed by, for example, exchanging the reaction solution or using a buffer solution as the reaction solution.
- Suitable buffers include glycine-HCl buffer, phosphate buffer, Tris-HCl buffer, acetate buffer, citrate buffer, citrate-phosphate buffer, borate buffer, tartrate buffer, glycine- A sodium hydroxide buffer solution etc. are mentioned.
- a solid neutralizing agent may be used in place of the buffer solution, and water may be used as the solvent. Examples thereof include calcium carbonate, chitosan, and deprotonated ion exchange resin. Neutralization can also be performed by appropriately adding an acid or alkali to the reaction solution. Moreover, you may add organic solvents, such as ethanol, as needed.
- the decomposition treatment by mixing and stirring the waste of the molded body of the biodegradable resin composition with the enzyme aqueous solution in the decomposition tank.
- the amount of the enzyme used varies depending on the activity of the enzyme used, but generally it may be an amount of about 0.01 to 10 parts by weight per 100 parts by weight of the hardly hydrolyzable biodegradable resin.
- the decomposition treatment is performed by putting the compact waste into the charged enzyme aqueous solution and stirring it.
- the solid acid catalyst since the solid acid catalyst contains water, the solid acid catalyst is dispersed in an appropriate organic solvent, and the compact waste is put into this dispersion. Is good.
- the biodegradable resin is decomposed into monomers or oligomers constituting the resin, and is taken out and used for microorganisms such as methane fermentation. Energy conversion may be performed, and if necessary, monomers or oligomers may be recovered by a separation operation such as distillation or extraction and reused for the synthesis of the biodegradable resin.
- ⁇ Analysis> GPC measurement using HFIP solvent For GPC, Tosoh Corporation was used, and HFIP-605 was used as a column. The temperature of the column oven was 40 ° C., HFIP (hexafluoroisopropanol) was used as the eluent, and the flow rate was 0.5 ml / min. The sample injection volume was 15 ⁇ l. As the standard, polymethyl methacrylate was dissolved in HFIP. For sample preparation, HFIP was used as a solvent to a concentration of 2 mg / ml and filtered.
- HFIP hexafluoroisopropanol
- Zeolite Zeon 3A (Ca type) manufactured by Union Showa Co., Ltd. was used. Chitosan (organic base): Wako Pure Chemical Industries, Ltd. was used.
- the CLE enzyme solution is Cryptococcus sp. a solution prepared by dissolving 20 mg of s-2 derived lipase (Independent Administrative Institution Liquor Research Institute: JP-A-2004-73123) powder in 1 ml of 0.05 M Tris-HCl buffer (pH 8.0) containing 50 w / w% glycerin; did.
- the decomposition solution was a solution obtained by adding 12 ⁇ l of CLE enzyme solution to 10 ml of 60 mmol / L phosphate buffer at pH 7.
- Enzymatic degradation test The film produced by the above method (2 cm ⁇ 2 cm, weight 70-80 mg) and 10 ml of the decomposition solution were placed in a 25 ml vial and shaken at 45 ° C. and 100 rpm for 6 days. In order to avoid an extreme decrease in pH, the 4 days were divided into 2 days and 2 days, and the decomposition solution was replaced. After 4 days, the film was taken out and dried in a 45 ° C. oven overnight, and the weight was measured. The amount of film degradation was determined by (initial film weight) ⁇ (film weight after 4 days).
- Examples 1 to 8 Comparative Examples 1 to 4> Various materials shown in Table 1 were blended at a predetermined blending ratio, and a film was prepared by the above-described molding method. Table 1 shows the results of the measurement of molecular weight retention of the obtained film and the enzymatic degradation test.
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Abstract
Description
この生分解性樹脂組成物に配合されているポリエチレンオキサレート等の脂肪族ポリエステルは、易加水分解性であり、水と混合したときに容易に加水分解して酸を放出するため、エステル分解促進剤として機能する。即ち、放出された酸により、生分解樹脂の加水分解が促進されるため、酵素による生分解性樹脂の分解を著しく促進することができる。また、この生分解性樹脂組成物により形成されている容器等の成形体を酵素水溶液と混合したときには、該脂肪族ポリエステルの加水分解によって成形体中に亀裂が発生することとなり、この結果、酵素が成形体の内部に容易に浸透するため、成形体の内部からも生分解性樹脂の分解が進行することとなり、この結果、成形加工品の形態でも酵素による生分解性樹脂の分解が著しく促進されるという利点がある。
本発明によれば、また、上記生分解性樹脂組成物を用いて成形された成形体が提供される。
(1)前記無機粒子がアルカリ金属またはアルカリ土類金属を含む塩基性化合物であること、
(2)前記塩基性化合物が炭酸カルシウムおよび/または炭酸ナトリウムであること、
(3)前記生分解性樹脂(A)100重量部当り、前記ポリグリコール酸(B)を0.01乃至30重量部の量で含有し、前記エステル分解促進助剤(C)を、前記ポリグリコール酸(B)100重量部当り、28乃至200重量部の量で含有していること、
が好ましい。
本発明において、用いる生分解性樹脂は、難加水分解性のものであり、例えば、生分解性樹脂を凍結粉砕し粉体化した試料で、10mg/10ml濃度の水分散液を作製し、45℃で一週間インキュベート後、残液のTOC(総有機炭素量)が5ppm以下であるものをいう。さらに水溶性のポリエステルは含まない。このような難加水分解性の生分解性樹脂の例としては、ポリ乳酸、ポリヒドロキシアルカノエート、ポリカプロラクトン、ポリブチレンサクシネート、酢酸セルロースなどを例示することができ、これらは共重合体やブレンド物の形で使用することもできる。
このような多価アルコールとしては、エチレングリコール、プロピレングリコール、ブタンジオール、オクタンジオール、ドデカンジオール、ネオペンチルグリコール、グリセリン、ペンタエリスリトール、ソルビタン、ポリエチレングリコールなどを例示することができる。
多塩基酸としては、シュウ酸、コハク酸、アジピン酸、セバシン酸、グルタル酸、デカンジカルボン酸、シクロヘキサンジカルボン酸、テレフタル酸を例示することができる。
ヒドロキシカルボン酸としては、グリコール酸、ヒドロキシプロピオン酸、ヒドロキシ吉草酸、ヒドロキシカプロン酸、マンデル酸を挙げることができる。
ラクトンとしては、カプロラクトン、ブチロラクトン、バレロラクトン、ポロピオラクトン、ウンデカラクトン、グリコリド、マンデライドなどを挙げることができる。
ポリグリコール酸(B)は、水分と混合したときにエステル分解の触媒として機能する酸を放出する易加水分解性のポリマーであり、生分解性樹脂(A)の全体にわたって均一に分散し、ポリグリコール酸(B)から放出される酸によっての生分解性樹脂(A)の加水分解を迅速に促進するために、例えば、その重量平均分子量が1000乃至500000程度のものが使用される。
エステル分解促進助剤(C)は、ポリグリコール酸(B)の加水分解を促進させるために使用される無機粒子であり、例えば、アルカリ金属またはアルカリ土類金属を含む塩基性化合物や、アルカリ金属やアルカリ土類金属のイオンを放出するゼオライトやイオン放出性フィラーが代表的である。即ち、このような無機粒子は、成形時および/または水の存在下でポリグリコール酸(B)の加水分解を促進する。
尚、上述した無機粒子の内、炭酸ナトリウムは、ポリグリコール酸(B)や生分解性樹脂(A)に対する加水分解促進機能が最も大きいが、このために、炭酸ナトリウムを単独で使用した場合には、熱成形時に生分解性樹脂(A)の分子量を極度に低下させ、さらには、生分解性樹脂(A)の変色等によりその製品価値が低下してしまうことがある。そこで、炭酸ナトリウムを用いる場合には、その量を生分解性樹脂(A)に対して0.1~35ppmの範囲とし、さらに、炭酸カルシウムと組み合わせて使用することが好ましく、これにより、成形時にポリグリコール酸の分解を促進しながらも、生分解性樹脂(A)の分子量低下を抑制でき、かつ、得られる生分解性樹脂組成物の酵素分解速度を上げることができる。このように、炭酸ナトリウムと炭酸カルシウムを併用した場合、そのトータルの配合量は、上述した範囲内、即ち、ポリグリコール酸(B)100重量部当り、28乃至200重量部、特に30乃至100重量部の範囲とするのがよい。
本発明の生分解性樹脂組成物は、上述した各成分以外に、各種の樹脂用添加剤を適宜配合することもでき、例えば、生分解性樹脂の成形性や生分解特性を損なわない量で、可塑剤、光安定剤、酸化防止剤、紫外線吸収剤、難燃剤、着色剤、顔料、充填材、離型剤、帯電防止剤、香料、発泡剤、抗菌・抗カビ剤、核形成材などを配合することができ、さらに必要に、他の熱可塑性樹脂をブレンドすることも可能である。
上述した各種成分を含む本発明の生分解性樹脂組成物は、上述した(A)~(C)の各成分を同時に混合し、各成分が分解しない程度の温度(例えば150℃乃至240℃程度)で押出機中で溶融混練することにより調製することができる。この場合、ポリグリコール酸(B)や(C)成分のエステル分解促進助剤と生分解性樹脂(A)とを同時に混合してもよいし、ポリグリコール酸(B)や(C)成分のエステル分解促進助剤各成分のマスターバッチを作製し、生分解性樹脂(A)と混合してもよい。
本発明の生分解性樹脂組成物を用いて成形された容器等の成形体は、廃棄に際しては、そのまま分解槽に供給してもよいが、これを適宜、裁断、圧潰等によって小片状にした後、分解槽に供給して分解処理される。
尚、前述した固体酸触媒を用いる場合には、固体酸触媒が含水しているため、適宜の有機溶媒中に固体酸触媒を分散しておき、この分散液に成形体廃棄物を投入するのがよい。
HFIP溶媒を用いたGPC測定;
GPCには、東ソー株式会社製を用い、カラムとしてHFIP-605を用いた。カラムオーブンの温度を40℃とし、溶離液としてHFIP(ヘキサフルオロイソプロパノール)を用い、流速を0.5ml/分とした。また、サンプル注入量は15μlとした。スタンダードはHFIPにポリメチルメタクリレートを溶解させ用いた。サンプル調整はHFIPを溶媒として濃度2mg/mlとし、フィルターろ過したものを用いた。
GPCには、東ソー株式会社製HLC-8120を用い、カラムとしてTSKgel SuperHM-H×2及びガードカラムとしてTSKguard column SuperH-Hを用いた。カラムオーブンの温度を40℃とし、溶離液としてクロロホルムを用い、流速を0.5ml/minとした。また、サンプル注入量は20μlとした。スタンダードはクロロホルムにポリスチレンを溶解させたものを用いた。サンプル調整はクロロホルムを溶媒として濃度3mg/mlとし、フィルターろ過したものを用いた。
ポリ乳酸(PLA):
natureworks社製4032D(d乳酸1.4±0.2%)を用いた。
ポリグリコール酸(PGA):
kureha社製のポリグリコール酸(重量平均分子量;10万、20万)を用いた。
炭酸カルシウム:
白石工業株式会社製brilliant1500(平均粒度;0.2μm)を用いた。
炭酸ナトリウム:
和光純薬工業製を用いた。
ゼオライト:
ユニオン昭和株式会社製ゼオライト3A(Ca型)を用いた。
キトサン(有機塩基):
和光純薬工業製を用いた。
各種材料をドライブレンドし、超小型混練機(株式会社東洋精機製作所製)で成形温度240℃及びスクリュー回転速度50rpmにて混練し、ペレットを作製した。該ペレットを240℃で5分間融解後、50~80Kgf/cm2の圧力で加熱加圧(ホットプレス)し、フィルムを作製した。
CLE酵素液の作製と分解液の作製;
CLE酵素液はCryptococcus sp. s-2由来リパーゼ(独立行政法人酒類総合研究所:特開2004-73123)粉末20mgを、50w/w%グリセリンを含む0.05MTris-HCl緩衝液(pH8.0)1mlに溶解させた液とした。分解液はpH7の60mmol/Lリン酸緩衝液10mlに、CLE酵素液12μlを添加した液とした。
酵素分解性試験;
上記方法で作製されたフィルム(2cm×2cm、重量70~80mg)と、上記分解液10mlを25mlのバイアル瓶内に入れ、45℃、100rpmで6日間振とうさせた。なお、pHの極度な低下を避けるため、4日間を2日、2日に分け、それぞれ分解液を交換して行った。4日後、フィルムを取り出し45℃オーブンで一晩乾燥させ、重量を測定した。フィルムの分解量は(初期のフィルム重量)―(4日後のフィルム重量)で求めた。
PLAと上記方法で作成したPLAフィルムに対してクロロホルム溶媒を用いたGPC測定を行った。PLAの分子量をMw(前)、作製したフィルムの分子量をMw(後)とし、分子量保持率をMw(後)/Mw(前)×100で求めた。分子量保持率が60%以上を○としている。
表1に示す各種材料を所定の配合比でブレンドし、上述の成形方法でフィルムを作成した。得られたフィルムの分子量保持率の測定、及び、酵素分解試験の結果を表1に示す。
Claims (5)
- 難加水分解性生分解性樹脂(A)、ポリグリコール酸(B)、及び該ポリグリコール酸の加水分解を促進する無機粒子からなるエステル分解促進助剤(C)を含むことを特徴とする生分解性樹脂組成物。
- 前記無機粒子がアルカリ金属またはアルカリ土類金属を含む塩基性化合物である請求項1に記載の生分解性樹脂組成物。
- 前記塩基性化合物が炭酸カルシウムおよび/または炭酸ナトリウムである請求項2に記載の生分解性樹脂組成物。
- 前記生分解性樹脂(A)100重量部当り、前記ポリグリコール酸(B)を0.01乃至30重量部の量で含有し、前記エステル分解促進助剤(C)を、前記ポリグリコール酸(B)100重量部当り、28乃至200重量部の量で含有している請求項1に記載の生分解性樹脂組成物。
- 請求項1に記載の生分解性樹脂組成物を用いて成形された成形体。
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EP2626386A1 (en) | 2013-08-14 |
RU2542249C2 (ru) | 2015-02-20 |
CA2813660A1 (en) | 2012-04-12 |
US20130184415A1 (en) | 2013-07-18 |
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