JP2009185108A - Solution of polylactic acid based resin - Google Patents
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本発明は、ポリ乳酸系共重合樹脂を溶剤に溶解したポリ乳酸系樹脂溶解物に関するものであり、さらには、Ｌ−ラクチドを合成するプロセスにおいて副生成するメソラクチドを有効に利用することを狙った、ポリ乳酸系樹脂溶解物に関する。このポリ乳酸系樹脂溶解物は、塗料・インキ・接着剤等の分野において、利用可能である。 The present invention relates to a polylactic acid-based resin dissolved material in which a polylactic acid-based copolymer resin is dissolved in a solvent, and further aims to effectively use meso-lactide generated as a by-product in the process of synthesizing L-lactide. The present invention relates to a dissolved polylactic acid resin. This polylactic acid resin melt can be used in the fields of paints, inks, adhesives and the like.
近年の環境問題に対する意識の高まりから、天然素材またはバイオマス由来原料からなる合成樹脂を利用した商品の開発が盛んに行われている。ポリ乳酸系樹脂もとうもろこし澱粉等のバイオマスを発酵させて得られるＬ−乳酸を合成原料として得ることができる樹脂であることから、各種用途開発が実施されている。 Due to the recent increase in awareness of environmental issues, the development of products using synthetic resins made of natural materials or biomass-derived materials has been actively conducted. Since the L-lactic acid obtained by fermenting biomass such as corn starch and the like is a synthetic raw material, various uses have been developed.
塗料・インキ・接着剤への展開を実施する場合、非晶性である必要があり、発明者らは、既に、ＤＬ−ラクチドを共重合させたポリ乳酸系樹脂溶解物を提案している。（特許文献１、２、３） When developing to paints, inks, and adhesives, it needs to be amorphous, and the inventors have already proposed a polylactic acid resin solution in which DL-lactide is copolymerized. (Patent Documents 1, 2, and 3)
上記ポリ乳酸系樹脂において、特に、ラクチド含有量が高い場合、樹脂溶解物の安定性が悪く、微量の樹脂析出物が発生するという欠点を有していた。樹脂析出物は１５℃以下程度の低温で保管すると発生しやすく、３〜６ヶ月保管で発生するという問題点がある。
本発明の課題は、低温保管時にも樹脂析出物の発生しにくい保存安定性に優れたポリ乳酸系樹脂溶解物を得ることである。 The subject of this invention is obtaining the polylactic acid-type resin melt | dissolution excellent in the storage stability which a resin deposit does not generate | occur | produce easily at the time of low temperature storage.
本発明者らは、鋭意検討の結果、Ｄ−乳酸を共重合させるための原料としてメソラクチドを使用した場合、ＤＬ−ラクチドを共重合させた場合と比較して、低温で長期保存した場合のポリ乳酸系樹脂溶解物の安定性が良好であること、すなわち、樹脂析出が抑制されることを発見し、本発明を完成させた。 As a result of intensive studies, the present inventors have found that when mesolactide is used as a raw material for copolymerizing D-lactic acid, compared with the case where DL-lactide is copolymerized, the polymer in the case of long-term storage at a low temperature is used. The present inventors completed the present invention by discovering that the stability of the lactic acid resin melt is good, that is, the resin precipitation is suppressed.
即ち、本発明は、以下の構成からなる。
（１） Ｄ−乳酸がメソラクチド由来であり、Ｌ−乳酸とＤ−乳酸のモル比（Ｌ／Ｄ）が１〜９の範囲にあり、乳酸残基含有量が５０重量％以上、還元粘度が０．２〜１．０ｄｌ／ｇの範囲にあるポリ乳酸系共重合樹脂（Ａ）と溶剤（Ｂ）を含有するポリ乳酸系樹脂溶解物。
（２） メソラクチドがバイオマス由来の発酵Ｌ−乳酸水溶液を原料とし、Ｌ−乳酸のオリゴマー化を経てＬ−ラクチドを合成するプロセスにおいて、ラセミ化により副生成され、Ｌ−ラクチドと蒸留精製により分離されたメソラクチドであることを特徴とする（１）記載のポリ乳酸系樹脂溶解物。
（３） 溶剤（Ｂ）がエステル系溶剤、ケトン系溶剤、芳香族系溶剤のいずれか少なくとも１種以上を含有することを特徴とする（１）または（２）に記載のポリ乳酸系樹脂溶解物。
（４） ポリ乳酸系共重合樹脂（Ａ）を構成する重合モノマーのうち、ラクチド以外の重合モノマーがε−カプロラクトンであり、ε−カプロラクトン共重合量が１０〜５０重量％の範囲にあることを特徴とする（１）または（２）に記載のポリ乳酸系樹脂溶解物。
（５） ポリ乳酸系共重合樹脂（Ａ）を構成する重合モノマーのうち、開環重合開始剤として、ポリグリセリンまたは／およびソルビトールを０．５〜１０重量％の範囲で共重合させたことを特徴とする（１）または（２）に記載のポリ乳酸系樹脂溶解物。
That is, this invention consists of the following structures.
(1) D-lactic acid is derived from meso lactide, the molar ratio of L-lactic acid to D-lactic acid (L / D) is in the range of 1 to 9, the lactic acid residue content is 50% by weight or more, and the reduced viscosity is A polylactic acid resin melt containing a polylactic acid copolymer resin (A) and a solvent (B) in the range of 0.2 to 1.0 dl / g.
(2) In the process of synthesizing L-lactide from biomass-derived fermentation L-lactic acid aqueous solution and synthesizing L-lactide through oligomerization of L-lactic acid, meso lactide is by-produced by racemization and separated from L-lactide by distillation purification. The dissolved polylactic acid resin according to (1), which is mesolactide.
(3) Solvent (B) contains at least one of an ester solvent, a ketone solvent, and an aromatic solvent, and dissolves the polylactic acid resin according to (1) or (2) object.
(4) Among the polymerization monomers constituting the polylactic acid copolymer resin (A), the polymerization monomer other than lactide is ε-caprolactone, and the amount of ε-caprolactone copolymerization is in the range of 10 to 50% by weight. The polylactic acid-based resin solution according to (1) or (2), which is characterized.
(5) Among the polymerization monomers constituting the polylactic acid copolymer resin (A), polyglycerin and / or sorbitol was copolymerized in the range of 0.5 to 10% by weight as a ring-opening polymerization initiator. The polylactic acid-based resin solution according to (1) or (2), which is characterized.
本発明によれば、低温で長期保存した場合にも樹脂析出物が発生しにくく樹脂溶解物の安定性が良好なポリ乳酸系樹脂溶解物を得ることができる。また、好ましい実施態様においては、残留ラクチドの除去が容易で塗膜の耐久性（耐加水分解性）が向上するという効果もある。 According to the present invention, it is possible to obtain a polylactic acid-based resin solution in which resin precipitates are hardly generated even when stored for a long time at a low temperature and the stability of the resin solution is good. Further, in a preferred embodiment, there is an effect that the residual lactide can be easily removed and the durability (hydrolysis resistance) of the coating film is improved.
本発明におけるポリ乳酸系共重合樹脂は、Ｌ−乳酸とＤ−乳酸のモル比（Ｌ／Ｄ）が１〜９であることも必要である。好ましくは、１〜５．６であり、更に好ましくは、１である。ラクチドとしては、メソラクチドのみを使用することが最も好ましい。本発明において、メソラクチドとはＬ−乳酸とＤ−乳酸の環状二量体のことである。 The polylactic acid copolymer resin in the present invention is required to have a molar ratio (L / D) of L-lactic acid to D-lactic acid of 1 to 9. Preferably, it is 1-5.6, More preferably, it is 1. As lactide, it is most preferable to use only mesolactide. In the present invention, mesolactide is a cyclic dimer of L-lactic acid and D-lactic acid.
Ｌ−乳酸とＤ−乳酸のモル比（Ｌ／Ｄ）が９を越えると、溶剤に対する溶解性が悪くなり、コーティング材用の原料樹脂溶液として使用できなくなる。 When the molar ratio (L / D) of L-lactic acid to D-lactic acid exceeds 9, the solubility in a solvent is deteriorated, and it cannot be used as a raw material resin solution for a coating material.
本発明におけるポリ乳酸系共重合樹脂において、ラクチド共重合量は、５０重量％以上である必要がある。５０重量％未満であると、コンポスト処理における生分解性が遅くなる。また、ポリＬ−乳酸フィルム等の成型品への密着性が低下し、コーティング材用原料としての有用性が低下する。 In the polylactic acid copolymer resin in the present invention, the lactide copolymerization amount needs to be 50% by weight or more. If it is less than 50% by weight, biodegradability in the composting process is delayed. Moreover, the adhesiveness to molded articles, such as a poly L-lactic acid film, falls, and the usefulness as a raw material for coating materials falls.
本発明におけるポリ乳酸系樹脂において、乳酸、ε−カプロラクトン以外の共重合成分としては、グリコール酸、２−ヒドロキシイソ酪酸、３−ヒドロキシ酪酸、１６−ヒドロキシヘキサデカン酸、２−ヒドロキシ−２−メチル酪酸、１０−ヒドロキシステアリン酸、リンゴ酸、クエン酸等のオキシ酸やコハク酸等のジカルボン酸、エチレングリコール、プロピレングリコール等のグリコール類が挙げられる。 In the polylactic acid resin in the present invention, as copolymerization components other than lactic acid and ε-caprolactone, glycolic acid, 2-hydroxyisobutyric acid, 3-hydroxybutyric acid, 16-hydroxyhexadecanoic acid, 2-hydroxy-2-methylbutyric acid Examples thereof include oxyacids such as 10-hydroxystearic acid, malic acid and citric acid, dicarboxylic acids such as succinic acid, and glycols such as ethylene glycol and propylene glycol.
本発明におけるポリ乳酸系共重合樹脂の還元粘度は、０．２〜１．０ｄｌ／ｇの範囲にある必要がある。還元粘度が０．２ｄｌ／ｇ未満の場合、分子量が低いため、得られる塗膜物性が弱すぎる。また、還元粘度が１．０ｄｌ／ｇを越える場合、溶液粘度が高すぎるため、コーティング適性が悪くなる。尚、当該還元粘度は、サンプル濃度０．１２５ｇ／２５ｍｌ、測定溶剤クロロホルム、測定温度２５℃でウベローデ粘度管を用いて測定した値である。 The reduced viscosity of the polylactic acid copolymer resin in the present invention needs to be in the range of 0.2 to 1.0 dl / g. When the reduced viscosity is less than 0.2 dl / g, the physical properties of the obtained coating film are too weak because the molecular weight is low. On the other hand, when the reduced viscosity exceeds 1.0 dl / g, the solution viscosity is too high and the coating suitability is deteriorated. The reduced viscosity is a value measured using an Ubbelohde viscosity tube at a sample concentration of 0.125 g / 25 ml, a measurement solvent chloroform and a measurement temperature of 25 ° C.
プラスチック塗料のようにスプレー塗装をするコーティング材の場合、ポリ乳酸系共重合樹脂の還元粘度は、０．２〜０．６ｄｌ／ｇであることが好ましい。 In the case of a coating material that is spray-painted like a plastic paint, the reduced viscosity of the polylactic acid copolymer resin is preferably 0.2 to 0.6 dl / g.
顔料を含むグラビアインキ用途の場合、ポリ乳酸系共重合樹脂の還元粘度は、０．３〜０．７ｄｌ／ｇの範囲にあることが好ましい。 In the case of gravure ink use including a pigment, the reduced viscosity of the polylactic acid-based copolymer resin is preferably in the range of 0.3 to 0.7 dl / g.
ドライラミネート接着剤用途の場合、ポリ乳酸系共重合樹脂の還元粘度は、０．４〜０．８ｄｌ／ｇの範囲にあることが好ましい。 In the case of a dry laminate adhesive, the reduced viscosity of the polylactic acid copolymer resin is preferably in the range of 0.4 to 0.8 dl / g.
本発明における溶剤（Ｂ）としては、エステル系溶剤、ケトン系溶剤、芳香族系溶剤のいずれか少なくとも１種以上を含有する必要があり、クロロホルム等のハロゲン系溶剤を含んではならない。本発明における溶剤（Ｂ）は、エステル系溶剤、ケトン系溶剤、芳香族系溶剤のいずれか少なくとも１種または２種以上からなるものであればさらに好ましい。 The solvent (B) in the present invention must contain at least one of an ester solvent, a ketone solvent, and an aromatic solvent, and must not contain a halogen solvent such as chloroform. The solvent (B) in the present invention is more preferably at least one or two or more of an ester solvent, a ketone solvent, and an aromatic solvent.
本発明におけるエステル系溶剤としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等が挙げられ、ケトン系溶剤としては、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノン等が挙げられ、芳香族系溶剤としては、トルエン、キシレン等が挙げられる。 Examples of ester solvents in the present invention include methyl acetate, ethyl acetate, propyl acetate, and butyl acetate. Examples of ketone solvents include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone. Examples of the group solvent include toluene and xylene.
本発明におけるε−カプロラクトンが共重合されたポリ乳酸系樹脂は、特に接着剤用途において有用であり、好ましくは１０〜２０重量％、特に好ましくは１０重量％程度共重合させることにより、ヒートシール材として有用なポリ乳酸系樹脂溶解物を得ることが出来る。また、ε−カプロラクトンを好ましくは３０〜４０重量％共重合させることにより、ドライラミネート用接着剤として有用な柔軟性を持った接着剤用原料とすることが出来る。 The polylactic acid-based resin copolymerized with ε-caprolactone in the present invention is particularly useful in adhesive applications, and is preferably 10 to 20% by weight, particularly preferably about 10% by weight, thereby heat-sealing material. A useful polylactic acid-based resin solution can be obtained. Further, by copolymerizing preferably 30 to 40% by weight of ε-caprolactone, it can be used as an adhesive raw material having flexibility that is useful as an adhesive for dry lamination.
本発明において、開環重合用開始剤として、ポリグリセリンまたは／およびソルビトールを０．５〜１０重量％の範囲で共重合させることが出来る。この開始剤を用いたポリ乳酸系樹脂は、プラスチック塗料、ドライラミネート接着剤、感圧接着剤等の硬化系樹脂塗膜が有用な場合に効果的である。硬化剤としては、多官能イソシアネート化合物が有効であり、特に、脂肪族系の多官能イソシアネートが有効である。 In the present invention, polyglycerin and / or sorbitol can be copolymerized in the range of 0.5 to 10% by weight as an initiator for ring-opening polymerization. The polylactic acid resin using this initiator is effective when a curable resin coating such as a plastic paint, a dry laminate adhesive, or a pressure sensitive adhesive is useful. As the curing agent, a polyfunctional isocyanate compound is effective, and an aliphatic polyfunctional isocyanate is particularly effective.
メソラクチドの入手経路としては、大規模プラントにおいて実施されているポリＬ−乳酸を生産するプロセスとして、Ｌ−乳酸水溶液を加熱脱水縮合させることにより、Ｌ−乳酸オリゴマーを得、反応系中に存在するＬ−ラクチドを得るプロセスにおいて、Ｌ−乳酸がラセミ化し、副生成してくるメソラクチドを使用するのが、経済合理性の観点からも優れている。 As a route for obtaining meso-lactide, an L-lactic acid oligomer is obtained by heat-dehydrating condensation of an aqueous L-lactic acid solution as a process for producing poly L-lactic acid, which is carried out in a large-scale plant, and is present in the reaction system. In the process of obtaining L-lactide, it is excellent from the viewpoint of economic rationality to use meso-lactide that is racemized and by-produced L-lactic acid.
さらに、メソラクチドを原料として使用すると、ＤＬ−ラクチドを使用するよりも、バッチ重合方式において、残留モノマーを減圧除去するのが容易であるという副次的な効果も見出している。ポリ乳酸系共重合樹脂から、残留するラクチドを除去すると、塗膜の耐久性（耐加水分解性）が向上するという効果もある。 Furthermore, when meso lactide is used as a raw material, a secondary effect has been found that it is easier to remove the residual monomer under reduced pressure in a batch polymerization method than when DL-lactide is used. When the remaining lactide is removed from the polylactic acid-based copolymer resin, there is an effect that the durability (hydrolysis resistance) of the coating film is improved.
以下、実施例にて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
実施例１
ポリ乳酸系樹脂Ａの重合：
Ｌ−ラクチド６００ｇ、メソラクチド４００ｇ、ソルビトール１０ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃に加熱、２時間開環重合をさせ、その後、未反応モノマーを減圧下留去させることにより、ポリ乳酸系樹脂Ａを得た。分析結果を表１に示す。
Example 1
Polymerization of polylactic acid resin A:
By adding 600 g of L-lactide, 400 g of meso lactide, 10 g of sorbitol and 250 mg of tin octylate to a flask, heating to 180 ° C. in a nitrogen atmosphere, carrying out ring-opening polymerization for 2 hours, and then distilling off unreacted monomers under reduced pressure. A polylactic acid resin A was obtained. The analysis results are shown in Table 1.
ポリ乳酸系樹脂Ａ溶解物の調製：
上記ポリ乳酸系樹脂Ａ５００ｇと酢酸エチル２５０ｇ、酢酸ブチル２５０ｇをフラスコに加え６０℃で５時間加熱撹拌することにより、ポリ乳酸系樹脂Ａ溶解物を得た。
Preparation of polylactic acid resin A lysate:
500 g of the above-mentioned polylactic acid-based resin A, 250 g of ethyl acetate and 250 g of butyl acetate were added to the flask and heated and stirred at 60 ° C. for 5 hours to obtain a polylactic acid-based resin A solution.
ポリ乳酸系樹脂Ａ溶解物の安定性評価：
ポリ乳酸系樹脂Ａ溶解物をガラス瓶に入れて密封し、５℃において、６ヶ月間静置保管し、外観を目視判定することにより評価を実施した。評価結果を表２に示す。
Stability evaluation of polylactic acid resin A dissolved product:
The polylactic acid-based resin A solution was put in a glass bottle and sealed, and stored at 5 ° C. for 6 months, and the appearance was evaluated by visual judgment. The evaluation results are shown in Table 2.
ポリ乳酸系樹脂Ａを用いた白塗料の調製および評価：
ポリ乳酸系樹脂Ａ溶解物１００ｇと酸化チタン（白顔料）５０ｇ、酢酸ブチル５０ｇをペイントシェーカーに加え、１時間分散することにより、白塗料を得た。評価結果を表３に示す。顔料分散性は、グロスメーターにて評価した。ポリＬ−乳酸製テストピースへの密着性は碁盤目を切り、セロテープ（登録商標）剥離により密着性を評価した。
Preparation and evaluation of white paint using polylactic acid resin A:
100 g of polylactic acid resin A dissolved material, 50 g of titanium oxide (white pigment), and 50 g of butyl acetate were added to a paint shaker and dispersed for 1 hour to obtain a white paint. The evaluation results are shown in Table 3. The pigment dispersibility was evaluated with a gloss meter. The adhesiveness to the test piece made of poly L-lactic acid was evaluated by cutting the grid and peeling the cello tape (registered trademark).
実施例２
ポリ乳酸系樹脂Ｂの重合：
Ｌ−ラクチド５００ｇ、メソラクチド４００ｇ、ε−カプロラクトン１００ｇ、ソルビトール１０ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃に加熱、２時間開環重合をさせ、その後、未反応モノマーを減圧下留去させることにより、ポリ乳酸系樹脂Ｂを得た。分析結果を表１に示す。
Example 2
Polymerization of polylactic acid resin B:
500 g of L-lactide, 400 g of meso lactide, 100 g of ε-caprolactone, 10 g of sorbitol and 250 mg of tin octylate are added to the flask, heated to 180 ° C. in a nitrogen atmosphere, and subjected to ring-opening polymerization for 2 hours, and then the unreacted monomer is reduced under reduced pressure. By distilling off, polylactic acid resin B was obtained. The analysis results are shown in Table 1.
ポリ乳酸系樹脂Ｂ溶解物の調製：
ポリ乳酸系樹脂Ｂ５００ｇと酢酸エチル５００ｇをフラスコに加え６０℃で５時間加熱撹拌することによりポリ乳酸系樹脂Ｂ溶解物を得た。
Preparation of polylactic acid resin B lysate:
A polylactic acid resin B solution was obtained by adding 500 g of polylactic acid resin B and 500 g of ethyl acetate to the flask and stirring with heating at 60 ° C. for 5 hours.
ヒートシール性の評価：
ポリ乳酸系樹脂Ｂ溶解物をポリＬ−乳酸フィルム（厚み２８μｍ）にドライ膜厚３μｍにて塗布し、６０℃で１５分間乾燥した後、未処理ポリＬ−乳酸フィルム（厚み２８μｍ）との貼り合わせを実施し、ヒートシール材としての評価を実施した。ヒートシールは、１００℃、０．９ｍ／分、３ｋｇｆ／ｃｍ２で実施した。結果を表４に示す。接着強度は引張試験機によるＴ型剥離試験により求めた。Ｔ型剥離試験は以下の条件で実施した；測定温度２０℃、サンプル幅１０ｍｍ、引張速度２０ｍｍ／分。
Evaluation of heat sealability:
The polylactic acid resin B dissolved material is applied to a poly L-lactic acid film (thickness 28 μm) at a dry film thickness of 3 μm, dried at 60 ° C. for 15 minutes, and then attached to an untreated poly L-lactic acid film (thickness 28 μm). Matching was performed and evaluation as a heat seal material was performed. Heat sealing was performed at 100 ° C., 0.9 m / min, and 3 kgf / cm 2. The results are shown in Table 4. The adhesive strength was determined by a T-type peel test using a tensile tester. The T-type peel test was carried out under the following conditions: measurement temperature 20 ° C., sample width 10 mm, tensile speed 20 mm / min.
実施例３
ポリ乳酸系樹脂Ｃの重合：
メソラクチド６００ｇ、ε−カプロラクトン４００ｇ、ソルビトール８ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃に加熱、２時間開環重合をさせ、その後、未反応モノマーを減圧下留去させることにより、ポリ乳酸系樹脂Ｃを得た。分析結果を表１に示す。
Example 3
Polymerization of polylactic acid resin C:
By adding 600 g of mesolactide, 400 g of ε-caprolactone, 8 g of sorbitol, and 250 mg of tin octylate to a flask under heating in a nitrogen atmosphere at 180 ° C. for 2 hours, and then distilling off unreacted monomers under reduced pressure. A polylactic acid resin C was obtained. The analysis results are shown in Table 1.
ポリ乳酸系樹脂Ｃ溶解物の調製：
ポリ乳酸系樹脂Ｃ５００ｇと酢酸エチル５００ｇをフラスコに加え６０℃で５時間加熱撹拌することによりポリ乳酸系樹脂Ｃ溶解物を得た
Preparation of polylactic acid resin C lysate:
A polylactic acid resin C melt was obtained by adding 500 g of polylactic acid resin C and 500 g of ethyl acetate to the flask and heating and stirring at 60 ° C. for 5 hours.
接着性の評価：
ポリ乳酸系樹脂Ｃ溶解物１００ｇと硬化剤（コロネートＨＸ、日本ポリウレタン（株）製、脂肪族イソシアネート化合物）５ｇを混合し、左記をドライ膜厚９μｍとなるようにポリＬ−乳酸フィルム（厚み２８μｍ）塗布し、６０℃で１５分間乾燥した。ついで、５０℃、０．９ｍ／分、３ｋｇｆ／ｃｍ２で未処理ポリＬ−乳酸フィルム（厚み２８μｍ）とドライラミネーションを実施し、４０℃にて３日間エージング後、接着強度の評価を実施した。評価結果を表４に示す。接着強度は引張試験機によるＴ型剥離試験により求めた。Ｔ型剥離試験は以下の条件で実施した；測定温度２０℃、サンプル幅１０ｍｍ、引張速度２０ｍｍ／分。
Evaluation of adhesion:
100 g of a polylactic acid resin C solution and 5 g of a curing agent (Coronate HX, manufactured by Nippon Polyurethane Co., Ltd., aliphatic isocyanate compound) are mixed, and the left is a poly L-lactic acid film (thickness 28 μm) so that the dry film thickness is 9 μm. ) And dried at 60 ° C. for 15 minutes. Next, dry lamination was performed with an untreated poly L-lactic acid film (thickness 28 μm) at 50 ° C., 0.9 m / min, 3 kgf / cm 2 , and after aging at 40 ° C. for 3 days, the adhesive strength was evaluated. . The evaluation results are shown in Table 4. The adhesive strength was determined by a T-type peel test using a tensile tester. The T-type peel test was carried out under the following conditions: measurement temperature 20 ° C., sample width 10 mm, tensile speed 20 mm / min.
比較例１
ポリ乳酸系樹脂Ｄの重合：
Ｌ−ラクチド６００ｇ、ＤＬ−ラクチド４００ｇ、ソルビトール２０ｇ、オクチル酸スズ２５０ｍｇをフラスコに加え、窒素雰囲気下、１８０℃に加熱、２時間開環重合をさせ、その後、未反応モノマーを減圧下留去させることにより、ポリ乳酸系樹脂Ｄを得た。分析結果を表１に示す。
Comparative Example 1
Polymerization of polylactic acid resin D:
Add 600 g of L-lactide, 400 g of DL-lactide, 20 g of sorbitol, and 250 mg of tin octylate to a flask, heat to 180 ° C. in a nitrogen atmosphere, cause ring-opening polymerization for 2 hours, and then distill off unreacted monomers under reduced pressure. As a result, a polylactic acid resin D was obtained. The analysis results are shown in Table 1.
ポリ乳酸系樹脂Ｄ溶解物の調製：
ポリ乳酸系樹脂Ｄ５００ｇと酢酸エチル２５０ｇ、酢酸ブチル２５０ｇをフラスコに加え６０℃で５時間加熱撹拌することによりポリ乳酸系樹脂Ｄ溶解物を得た。
Preparation of polylactic acid resin D lysate:
A polylactic acid resin D solution was obtained by adding 500 g of polylactic acid resin D, 250 g of ethyl acetate, and 250 g of butyl acetate to the flask and stirring with heating at 60 ° C. for 5 hours.
ポリ乳酸系樹脂Ｄ溶解物の安定性評価：
ポリ乳酸系樹脂Ｄ溶解物をガラス瓶に入れて密封し、５℃において、６ヶ月間静置保管し、外観を目視判定することにより評価を実施した。評価結果を表２に示す。
Stability evaluation of polylactic acid resin D dissolved product:
The polylactic acid-based resin D solution was put in a glass bottle, sealed, stored at 5 ° C. for 6 months, and evaluated by visually judging the appearance. The evaluation results are shown in Table 2.
本発明の乳酸系樹脂溶解物は、コーティング剤、インキ、接着剤等の用途に使用できる。特に、プラスチック塗料のようにスプレー塗装をするコーティング材、顔料を含むグラビアインキ、ドライラミネート接着剤等に有用である。
The lactic acid resin melt of the present invention can be used for applications such as coating agents, inks, and adhesives. In particular, it is useful for coating materials for spray painting such as plastic paints, gravure inks containing pigments, dry laminate adhesives, and the like.
Claims (5)
Of the polymerization monomers constituting the polylactic acid copolymer resin (A), polyglycerin and / or sorbitol is copolymerized in the range of 0.5 to 10% by weight as a ring-opening polymerization initiator. The polylactic acid-based resin solution according to claim 1 or 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011252102A (en) * | 2010-06-03 | 2011-12-15 | Konishi Co Ltd | Polylactic acid-based adhesive and method for producing the same |
| JP2015165007A (en) * | 2014-02-06 | 2015-09-17 | 株式会社リコー | Polylactic acid resin fine particle |
| JP2016050292A (en) * | 2014-09-02 | 2016-04-11 | 東洋紡株式会社 | Polylactic acid-based resin for pulverized toner, polylactic acid-based resin composition for pulverized toner, and pulverized toner using these |
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| JPH01146924A (en) * | 1987-10-28 | 1989-06-08 | Cca Biochem Bv | Polymerlactide, its production and composition containing the same |
| JPH08301864A (en) * | 1995-05-09 | 1996-11-19 | Toyobo Co Ltd | Purification of intermolecular cyclic diester of alpha-oxyacid |
| JPH11263830A (en) * | 1989-11-09 | 1999-09-28 | Boehringer Ingelheim Kg | New copolymer comprising trimethylene carbonate and optically inert lactide |
| WO2007088135A1 (en) * | 2006-01-31 | 2007-08-09 | Purac Biochem Bv | Method for the purification of resorbable polymers from residual monomers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01146924A (en) * | 1987-10-28 | 1989-06-08 | Cca Biochem Bv | Polymerlactide, its production and composition containing the same |
| JPH11263830A (en) * | 1989-11-09 | 1999-09-28 | Boehringer Ingelheim Kg | New copolymer comprising trimethylene carbonate and optically inert lactide |
| JPH08301864A (en) * | 1995-05-09 | 1996-11-19 | Toyobo Co Ltd | Purification of intermolecular cyclic diester of alpha-oxyacid |
| WO2007088135A1 (en) * | 2006-01-31 | 2007-08-09 | Purac Biochem Bv | Method for the purification of resorbable polymers from residual monomers |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011252102A (en) * | 2010-06-03 | 2011-12-15 | Konishi Co Ltd | Polylactic acid-based adhesive and method for producing the same |
| JP2015165007A (en) * | 2014-02-06 | 2015-09-17 | 株式会社リコー | Polylactic acid resin fine particle |
| JP2016050292A (en) * | 2014-09-02 | 2016-04-11 | 東洋紡株式会社 | Polylactic acid-based resin for pulverized toner, polylactic acid-based resin composition for pulverized toner, and pulverized toner using these |
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