JP2007138062A - Polylactic acid-based resin composition - Google Patents
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本発明は、難燃性、成形性に優れたポリ乳酸系樹脂組成物に関する。 The present invention relates to a polylactic acid resin composition having excellent flame retardancy and moldability.
近年、石油事情、また環境問題といった観点から、従来の合成樹脂製品はリサイクル、リユースされるようになってきている。主に魚箱、家電緩衝材、食品用トレー等に使用される発泡スチロール（発泡ポリスチレン）も例外ではなく、破砕減容して主にマテリアルリサイクルされるようになってきている。 In recent years, conventional synthetic resin products have been recycled and reused from the viewpoints of petroleum circumstances and environmental problems. Styrofoam (foamed polystyrene) used mainly for fish boxes, home appliance cushioning materials, food trays, etc. is no exception, and has been crushed and reduced in volume and is mainly being recycled.
しかし、こういったマテリアルリサイクルの試みは卸売市場で発生する使用済み魚箱、大型家電の緩衝材等、使用済みのものの回収が容易なものに限られており、一般小売業者、飲食店で発生するものや末端消費者が直接自宅に持ち帰る商品に使用されているものの回収率は極めて低い。 However, such material recycling attempts are limited to items that are easy to collect used items such as used fish boxes and large home appliance cushions in the wholesale market, and are generated at general retailers and restaurants. The recovery rate is extremely low for products that are used and products that are directly used by end consumers to take home.
回収が困難な発泡スチロール製品は一般ゴミと一緒に廃棄されることが多いが、相応の設備を有しない焼却処分場では、その高い燃焼熱ゆえに焼却炉を傷めてしまう。 Styrofoam products that are difficult to recover are often discarded together with general waste, but incinerators that do not have the appropriate equipment will damage the incinerator due to the high combustion heat.
これらの状況に鑑み、燃焼熱が低く炉を傷めず、しかも微生物による分解が可能な発泡成形体として、ポリ乳酸系樹脂発泡体及びその成形体が、特許文献１で開示されている。 In view of these circumstances, Patent Document 1 discloses a polylactic acid resin foam and its molded body as a foamed molded body that has low combustion heat and does not damage the furnace and can be decomposed by microorganisms.
しかし、特許文献１のポリ乳酸系樹脂発泡成形体は難燃性については言及されておらず、難燃性が無いことが予測される。 However, the polylactic acid-based resin foam molded article of Patent Document 1 is not mentioned about flame retardancy, and is expected to have no flame retardancy.
特許文献２には、尿素、リン酸アンモニウム、ポリリン酸アンモニウム、グアニジン系の化合物が生分解性樹脂の、非発泡の成形体において、難燃剤として有効に機能することが記載されている。しかし、特許文献２では発泡体に触れておらず、難燃剤の添加量が２０〜８０重量部と多く、特許文献２記載の樹脂をそのまま発泡体に適用しても、発泡体の気泡壁に悪影響をおよぼして破泡が発生しやすくなる為、成形性が著しく悪化し良好な外観を有する発泡成形体が得られない。 Patent Document 2 describes that urea, ammonium phosphate, ammonium polyphosphate, and guanidine-based compounds function effectively as flame retardants in non-foamed molded articles of biodegradable resins. However, in Patent Document 2, the foam is not touched, the amount of flame retardant added is as large as 20 to 80 parts by weight, and even if the resin described in Patent Document 2 is applied to the foam as it is, Since foaming is likely to occur due to adverse effects, moldability is remarkably deteriorated and a foamed molded article having a good appearance cannot be obtained.
特許文献３にはハロゲン系、リン系、ケイ素系、無機系化合物が生分解性樹脂の押出発泡体において、難燃剤として有効に機能することが記載されている。 Patent Document 3 describes that halogen-based, phosphorus-based, silicon-based, and inorganic compounds function effectively as flame retardants in extruded foams of biodegradable resins.
しかし、特許文献３は発泡剤として熱分解型発泡剤のみが開示されているが、熱分解型発泡剤は発泡温度が比較的高温となるため、熱分解温度が低いポリ乳酸系樹脂のような生分解性樹脂においては、特許文献２と同様に発泡体の気泡壁に悪影響をおよぼし破泡が発生しやすくなる為、成形性が著しく悪化し良好な外観を有する発泡成形体が得られない。
本発明が解決しようとする課題は、優れた難燃性、成形性を有するポリ乳酸系樹脂組成物を提供することにある。 The problem to be solved by the present invention is to provide a polylactic acid resin composition having excellent flame retardancy and moldability.
本発明者らは上述の課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed the present invention.
即ち、本発明の第１は、乳酸成分の異性体比率（Ｌ体／Ｄ体）が、９２／８〜８／９２であるポリ乳酸系樹脂１００重量部に対し、ポリイソシアネート化合物を１重量部以上５重量部以下含み、且つリン系化合物を３重量部以上１０重量部以下含むポリ乳酸系樹脂組成物に関する。 That is, according to the first aspect of the present invention, 1 part by weight of a polyisocyanate compound is used per 100 parts by weight of a polylactic acid resin having an isomer ratio (L-form / D-form) of the lactic acid component of 92/8 to 8/92. The present invention relates to a polylactic acid resin composition containing 5 parts by weight or less and 3 parts by weight or more and 10 parts by weight or less of a phosphorus compound.
好ましい実施態様としては、リン系化合物がアンモニウムポリホスフェートである前記記載のポリ乳酸系樹脂組成物に関し、別の好ましい態様としては、前記記載のポリ乳酸系樹脂に発泡剤として炭素数５以下の炭化水素類を含浸させた発泡性ポリ乳酸系樹脂組成物に関する。 A preferred embodiment relates to the polylactic acid resin composition described above, wherein the phosphorus compound is ammonium polyphosphate. Another preferred embodiment is carbonization of 5 or less carbon atoms as a blowing agent in the polylactic acid resin described above. The present invention relates to a foamable polylactic acid resin composition impregnated with hydrogen.
本発明の第２は、前記記載の発泡性ポリ乳酸系樹脂組成物からなるポリ乳酸系樹脂発泡粒子に関し、本発明の第３は、前記記載のポリ乳酸系樹脂発泡粒子からなるポリ乳酸系樹脂発泡成形体に関する。 2nd of this invention is related with the polylactic acid-type resin expanded particle which consists of said foamable polylactic acid-type resin composition, and 3rd of this invention is polylactic acid-type resin which consists of said polylactic acid-type resin expanded particle. The present invention relates to a foam molded article.
本発明により、優れた難燃性、成形性を有するポリ乳酸系樹脂組成物を提供することができる。 According to the present invention, a polylactic acid resin composition having excellent flame retardancy and moldability can be provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に使用するポリ乳酸系樹脂としては、結晶性の高い樹脂は発泡ガスを含浸する際や、予備発泡をする際に結晶化し、発泡性、成形性を阻害する為、乳酸成分の異性体比率（Ｌ体／Ｄ体）が、９２／８〜８／９２、好ましくは９０／１０〜１０／９０のものが用いられる。 As the polylactic acid resin used in the present invention, a highly crystalline resin is crystallized when impregnated with a foaming gas or pre-foamed to inhibit foamability and moldability. The ratio (L-form / D-form) is 92/8 to 8/92, preferably 90/10 to 10/90.
本発明のポリ乳酸系樹脂組成物は、ポリイソシアネート化合物を含んでなる。 The polylactic acid resin composition of the present invention comprises a polyisocyanate compound.
例示されるポリイソシアネート化合物としては芳香族ポリイソシアネート、脂環族ポリイソシアネート、脂肪族ポリイソシアネー等がある。例えば、芳香族ポリイソシアネートとしては、トリレン、ジフェニルメタン、ナフチレン、トリフェニルメタンを骨格とするポリイソシアネート化合物がある。また、脂環族ポリイソシアネートとしては、イソホロン、水酸化ジフェニルメタンを骨格とするポリイソシアネート化合物がある。また、脂肪族ポリイソシアネートとしてはヘキサメチレン、リジンを骨格とするポリイソシアネート化合物がある。これらはいずれも使用可能であるが、汎用性、ハンドリング性等から芳香族ポリイソシアネートが好ましく、さらに好ましくはトリレン、ジフェニルメタン系のポリイソシアネート、特に好ましくはジフェニルメタン系ポリイソシアネートが使用される。 Examples of the polyisocyanate compound include aromatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate. For example, aromatic polyisocyanates include polyisocyanate compounds having skeletons of tolylene, diphenylmethane, naphthylene, and triphenylmethane. Moreover, as alicyclic polyisocyanate, there exists a polyisocyanate compound which makes isophorone and diphenylmethane hydroxide frame | skeleton. Examples of the aliphatic polyisocyanate include polyisocyanate compounds having hexamethylene and lysine as a skeleton. Any of these can be used, but aromatic polyisocyanates are preferred from the viewpoint of versatility and handling properties, more preferably tolylene and diphenylmethane-based polyisocyanates, and particularly preferably diphenylmethane-based polyisocyanates.
ポリイソシアネート化合物の添加量は、ポリ乳酸系樹脂１００重量部に対して１重量部以上５重量部以下であり、好ましくは１重量部以上３重量部以下である。ポリイソシアネート化合物の添加量が１重量部以上であれば、ポリ乳酸系樹脂組成物に７０℃以上９０℃以下の発泡温度域で良好な発泡性を示す為に必要な粘度を付与することができ、５重量部以下にすることで、発泡性を阻害することのない粘度を付与することができる。 The addition amount of the polyisocyanate compound is 1 part by weight or more and 5 parts by weight or less, preferably 1 part by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the polylactic acid resin. If the addition amount of the polyisocyanate compound is 1 part by weight or more, the polylactic acid resin composition can be given a viscosity necessary for exhibiting good foamability in a foaming temperature range of 70 ° C. to 90 ° C. By setting it to 5 parts by weight or less, it is possible to impart a viscosity that does not hinder foamability.
本発明に使用されるリン系化合物は、分子中にリン原子を有するものであれば特に制限は無く、例えば三酸化リン、四酸化リン、五酸化リン等のリン酸化物、リン酸、亜リン酸、次亜リン酸、メタリン酸、ピロリン酸、ポリリン酸等のリン酸化合物、モノアンモニウムホスフェート、ジアンモニウムホスフェート、アンモニウムポリホスフェート等のリン酸アンモニウム塩、メラミンホスフェート、メラミンジホスフェート、メラミンポリホスフェート等のリン酸メラミン塩、リン酸リチウム、リン酸ナトリウム、リン酸カリウム、リン酸カルシウム、リン酸マグネシウム等のリン酸金属塩等のリン酸塩類、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ（２−エチルヘキシル）ホスフェート、トリブトキシエチルホスフェート、モノイソデシルホスフェート、２−アクリロイルオキシエチルアシッドホスフェート、２メタクリロイルオキエチルアシッドホスフェート等の脂肪族系リン酸エステル類、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス（イソプロリルフェニル）ホスフェート、トリナフチルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、ジフェニル（２−エチルヘキシル）ホスフェート、ジ（イソプロピルフェニル）フェニルホスフェート、ジフェニル−２−アクリロイルオキシエチルホスフェート、ジフェニル−２−メタクリロイルオキシエチルホスフェート等の芳香族系リン酸エステル類等が挙げられる。これらはいずれも使用可能であるが、汎用性、ハンドリング性等からリン酸アンモニウム塩類が好ましく、特に好ましくはアンモニウムポリホスフェートが使用される。 The phosphorus compound used in the present invention is not particularly limited as long as it has a phosphorus atom in the molecule. For example, phosphorus oxides such as phosphorus trioxide, phosphorus tetroxide, phosphorus pentoxide, phosphoric acid, phosphorous acid Phosphate compounds such as acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, ammonium phosphate salts such as monoammonium phosphate, diammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine diphosphate, melamine polyphosphate, etc. Phosphoric acid salts such as melamine phosphate, lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) Phosphate, Tribute Aliphatic phosphate esters such as ciethyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2methacryloyl oxyethyl acid phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopro Rylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyl And aromatic phosphates such as oxyethyl phosphate. Any of these can be used, but ammonium phosphates are preferable from the viewpoint of versatility and handling properties, and ammonium polyphosphate is particularly preferably used.
リン系化合物の添加量は、ポリ乳酸系樹脂１００重量部に対して３重量部以上１０重量部以下であり、好ましくは５重量部以上７重量部以下である。リン系化合物の添加量を３重量部以上にすることで、十分な難燃性を有するポリ乳酸系発泡成形体が得られ、１０重量部以下であれば、良好な成形性を有する。 The addition amount of the phosphorus compound is 3 to 10 parts by weight, preferably 5 to 7 parts by weight, based on 100 parts by weight of the polylactic acid resin. By setting the addition amount of the phosphorus compound to 3 parts by weight or more, a polylactic acid-based foam molded article having sufficient flame retardancy can be obtained, and if it is 10 parts by weight or less, good moldability is obtained.
本発明のポリ乳酸系樹脂組成物には、発泡セルの均一化、細孔化を目的として、無機粉体等の気泡調整剤（発泡核剤）を添加しても良い。具体的には、タルク、雲母、粘土鉱物、炭酸カルシウム、炭酸水素ナトリウム、クエン酸等が使用可能であるが、特にこれらに限定されるものではない。 To the polylactic acid resin composition of the present invention, an air conditioner (foaming nucleating agent) such as an inorganic powder may be added for the purpose of making the foamed cells uniform and making the pores fine. Specifically, talc, mica, clay mineral, calcium carbonate, sodium hydrogen carbonate, citric acid and the like can be used, but are not particularly limited thereto.
また、本発明のポリ乳酸系樹脂組成物中には、帯電防止剤、着色剤、酸化防止剤、熱安定剤、紫外線吸収剤等の各種添加剤を含んでいてもよい。 The polylactic acid resin composition of the present invention may contain various additives such as an antistatic agent, a colorant, an antioxidant, a heat stabilizer, and an ultraviolet absorber.
本発明のポリ乳酸系樹脂組成物を得るには公知の方法が使用可能であり、例えば単軸又は二軸混練機で溶融混練する方法等があるが、特に二軸混練機で溶融混練する方法が好適に使用される。又、溶融状態のポリ乳酸系樹脂組成物を粒子化する方法としては、例えばストランドカットや水中カットによって粒子化する方法等があるが、特に水中カットによって粒子化する方法が好適に使用される。 In order to obtain the polylactic acid resin composition of the present invention, a known method can be used, for example, a method of melt kneading with a single screw or twin screw kneader, etc. Are preferably used. In addition, as a method for forming a molten polylactic acid resin composition into particles, for example, there are a method of forming particles by strand cutting or underwater cutting, and the method of forming particles by underwater cutting is particularly preferably used.
本発明の発泡性ポリ乳酸系樹脂組成物は、粒子化されたポリ乳酸系樹脂組成物と発泡剤、分散媒としての水を密閉容器内に充填し、ポリ乳酸系樹脂組成物の軟化温度以上に加熱した後、十分に冷却後取り出すことにより得られる。 The foamable polylactic acid-based resin composition of the present invention is filled with a particulate polylactic acid-based resin composition, a foaming agent, and water as a dispersion medium in a hermetically sealed container, and exceeds the softening temperature of the polylactic acid-based resin composition. It is obtained by taking out after cooling sufficiently after heating.
発泡性ポリ乳酸系樹脂組成物を得る為に、発泡剤として炭素数５以下の炭化水素類、例えば、エタン、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン等を使用することが好ましい。さらに好ましくは、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタンが使用される。炭素数が５以下の炭化水素類を発泡剤として使用することで、十分な発泡性且つ良好な外観を有する発泡成形体が得られ易い。 In order to obtain a foamable polylactic acid-based resin composition, it is preferable to use hydrocarbons having 5 or less carbon atoms, for example, ethane, propane, normal butane, isobutane, normal pentane, isopentane, etc. as a foaming agent. More preferably, normal butane, isobutane, normal pentane and isopentane are used. By using hydrocarbons having 5 or less carbon atoms as the foaming agent, it is easy to obtain a foamed molded article having sufficient foamability and good appearance.
又、発泡剤は２種類以上を併用しても良い。さらに、発泡剤の添加量は粒子化されたポリ乳酸系樹脂組成物１００重量部に対して４重量部以上が好ましい。発泡剤の添加量を４重量部以上にすることで十分な発泡性且つ良好な外観を有する発泡成形体が得られ易い。 Two or more foaming agents may be used in combination. Furthermore, the addition amount of the foaming agent is preferably 4 parts by weight or more with respect to 100 parts by weight of the polylactic acid-based resin composition that has been made into particles. By setting the addition amount of the foaming agent to 4 parts by weight or more, it is easy to obtain a foamed molded article having sufficient foamability and good appearance.
発泡剤を含浸する時に樹脂の分散性を改善し、膠着を防ぐ目的で分散助剤を添加しても良い。分散助剤としてはポリビニルアルコール、ポリビニルピロリドン、多糖類等の高分子物質を使用することも可能であるが、界面活性剤、特に非イオン系界面活性剤が好適に使用される。 When impregnating the foaming agent, a dispersion aid may be added for the purpose of improving the dispersibility of the resin and preventing sticking. As the dispersion aid, a polymer substance such as polyvinyl alcohol, polyvinyl pyrrolidone, and polysaccharide can be used, but a surfactant, particularly a nonionic surfactant, is preferably used.
例えば、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンパルミチルエーテル等のポリオキシエチレンアルキルエーテル類やＴｗｅｅｎ２０（商標）、Ｔｗｅｅｎ４０（商標）、Ｔｗｅｅｎ６０（商標）、Ｔｗｅｅｎ８０（商標）等のポリオキシエチレンソルビタン脂肪酸エステル類、Ｓｐａｎ２０（商標）、Ｓｐａｎ６０（商標）、Ｓｐａｎ８０（商標）等のソルビタン脂肪酸エステル類等が挙げられる。 For example, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene palmityl ether, and polyoxyethylene sorbitan fatty acid esters such as Tween20 (trademark), Tween40 (trademark), Tween60 (trademark), and Tween80 (trademark) And sorbitan fatty acid esters such as Span20 (trademark), Span60 (trademark) and Span80 (trademark).
さらに、発泡剤含浸時に着色成分や機能性を付与する成分を含浸しても良い。例えば、帯電防止剤、芳香剤、消臭剤、防腐剤、抗菌剤、各種着色剤などがあげられる。 Furthermore, you may impregnate the coloring component and the component which provides functionality at the time of a foaming agent impregnation. For example, antistatic agents, fragrances, deodorants, antiseptics, antibacterial agents, various colorants and the like can be mentioned.
本発明のポリ乳酸系樹脂発泡粒子を得る方法は、発泡性ポリ乳酸系樹脂組成物を水蒸気や熱風、高周波等によって発泡させる方法が適用できるが、発泡スチロール用の予備発泡機を用いる方法が最も簡便で一般的である。 As a method for obtaining the polylactic acid-based resin expanded particles of the present invention, a method of foaming a foamable polylactic acid-based resin composition with water vapor, hot air, high frequency, or the like can be applied, but a method using a pre-foaming machine for expanded polystyrene is the simplest. Is common.
本発明のポリ乳酸系樹脂発泡成形体を得る方法は、ポリ乳酸系発泡粒子を発泡スチロールや発泡ポリエチレン、発泡ポリプロピレン等の成形に用いる成形機によって成形する方法が最も簡便で一般的であるが、予備発泡の工程を経ず、金型内で発泡と成形を同時に行うこともできる。 As a method for obtaining the polylactic acid resin foamed molded article of the present invention, a method of molding polylactic acid-based foamed particles with a molding machine used for molding foamed polystyrene, foamed polyethylene, foamed polypropylene or the like is the simplest and common. It is also possible to perform foaming and molding simultaneously in the mold without going through the foaming step.
以下、実施例によって本発明を詳細に説明するが、本発明は、これらの実施例に何ら限定されるものではない。尚、評価は下記の方法で行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples at all. The evaluation was performed by the following method.
（評価方法）
（１）発泡倍率の測定方法：内容積２０００ｃｍ３のポリエチレン製カップに発泡粒子を擦切り一杯量り取り、重量を測定し、風袋重量を差引いて発泡粒子の重量をもとめた。発泡倍率は、発泡粒子の重量と見かけ体積（２０００ｃｍ３）から下記の式により求めた。
発泡倍率＝見かけ体積（２０００ｃｍ３）／発泡粒子の重量（ｇ）
(Evaluation methods)
(1) Method for measuring expansion ratio: The foamed particles were scraped and weighed into a polyethylene cup having an internal volume of 2000 cm 3 and weighed. The tare weight was subtracted to determine the weight of the expanded particles. The expansion ratio was determined by the following formula from the weight of the expanded particles and the apparent volume (2000 cm 3 ).
Expansion ratio = apparent volume (2000 cm 3 ) / weight of expanded particles (g)
（２）成形性の評価方法：型内成形を行い以下の基準で目視にて評価した。
○：良好
×：不良
(2) Formability evaluation method: In-mold molding was performed and visually evaluated according to the following criteria.
○: Good ×: Bad
（３）難燃性の評価方法：ＪＩＳ Ａ ９５１１（発泡プラスチック保温材）４．１３．１測定方法Ａに準じた評価を行った。
○：消火時間が３秒以内。
×：消火時間が３秒を超える或いは消火しなかった。
(3) Flame retardancy evaluation method: Evaluation according to JIS A 9511 (foamed plastic heat insulating material) 4.13.1 measurement method A was performed.
○: Fire extinguishing time is within 3 seconds.
X: Fire extinguishing time exceeded 3 seconds or did not extinguish.
（実施例１）
乳酸成分の異性体比率（Ｌ体／Ｄ体）が９０／１０であるポリ乳酸樹脂１００重量部に対してアンモニウムポリホスフェート「ペコフレームＴＣ−２０４」（クラリアントジャパン（株）製）を３重量部ドライブレンドし、ポリイソシアネート化合物「ミリオネートＭＲ−２００」（日本ポリウレタン工業（株）製）を２重量部添加しつつ２軸混練機「ＴＥＭ−３５Ｂ」（東芝機械（株）製）にてシリンダ温度１８５℃で溶融混練し、水中カッターを用いて約１ｍｍφに粒子化されたポリ乳酸系樹脂組成物を得た。得られたポリ乳酸樹脂組成物を１００重量部、水１００重量部、発泡剤として混合ブタン（ノルマルブタン／イソブタン＝７０／３０）２５重量部とを密閉容器に充填し、９４℃で９０分間保持し、発泡剤を含浸させた。十分に冷却後取り出し、乾燥して発泡性ポリ乳酸系樹脂組成物を得た。得られた発泡性ポリ乳酸樹脂粒子を発泡スチロール用予備発泡機「ＤＹＨＬ−３００」（ダイセン工業（株））にて発泡温度８８℃で発泡させ、ポリ乳酸系樹脂発泡粒子を得た。さらに、得られたポリ乳酸系樹脂発泡粒子を２４時間以上常温で保管・熟成後、発泡スチロール用成形機「ＶＳ−３００Ｌ−ＭＣ」（ダイセン工業（株））にて、３００ｍｍ×３００ｍｍ×３０ｍｍのポリ乳酸系樹脂発泡成形体を得た。得られた発泡成形体の難燃性の評価を行った。
Example 1
3 parts by weight of ammonium polyphosphate “Peco Flame TC-204” (manufactured by Clariant Japan Co., Ltd.) with respect to 100 parts by weight of polylactic acid resin in which the isomer ratio of lactic acid component (L-form / D-form) is 90/10 Cylinder temperature in a twin-screw kneader “TEM-35B” (Toshiba Machine Co., Ltd.) while adding 2 parts by weight of the polyisocyanate compound “Millionate MR-200” (Nippon Polyurethane Industry Co., Ltd.) A polylactic acid resin composition was obtained by melt-kneading at 185 ° C. and granulated to about 1 mmφ using an underwater cutter. 100 parts by weight of the obtained polylactic acid resin composition, 100 parts by weight of water, and 25 parts by weight of mixed butane (normal butane / isobutane = 70/30) as a blowing agent are filled in a sealed container and kept at 94 ° C. for 90 minutes. And impregnated with a blowing agent. After sufficiently cooling, the product was taken out and dried to obtain a foamable polylactic acid resin composition. The foamable polylactic acid resin particles obtained were foamed at a foaming temperature of 88 ° C. with a pre-foaming machine for styrene foam “DYHL-300” (Daisen Industrial Co., Ltd.) to obtain polylactic acid resin foamed particles. Furthermore, the obtained polylactic acid-based resin expanded particles were stored and aged at room temperature for 24 hours or more, and then a 300 mm × 300 mm × 30 mm polystyrene was formed with a polystyrene molding machine “VS-300L-MC” (Daisen Industrial Co., Ltd.). A lactic acid resin foam molded article was obtained. The obtained foamed molded product was evaluated for flame retardancy.
（実施例２、３）
アンモニウムポリホスフェートの添加量をそれぞれ５重量部（実施例２）及び１０重量部（実施例３）としたこと以外は実施例１と同様にして得られたポリ乳酸系樹脂発泡成形体の難燃性の評価を行った。
(Examples 2 and 3)
Flame retardant of polylactic acid resin foam molded article obtained in the same manner as in Example 1 except that the amount of ammonium polyphosphate added was 5 parts by weight (Example 2) and 10 parts by weight (Example 3), respectively. Sexuality was evaluated.
（実施例４）
乳酸成分の異性体比率（Ｌ体／Ｄ体）が８８／１２であるポリ乳酸樹脂を使用したこと以外は実施例２と同様にして得られたポリ乳酸系樹脂発泡成形体の難燃性の評価を行った。
Example 4
The flame-retardant property of the polylactic acid-based resin foam molded article obtained in the same manner as in Example 2 except that a polylactic acid resin having an isomer ratio (L-form / D-form) of 88/12 is used. Evaluation was performed.
（実施例５）
ポリイソシアネート化合物の添加量を５重量部としたこと以外は実施例２と同様にして得られたポリ乳酸系樹脂発泡成形体の難燃性の評価を行った。
(Example 5)
The flame retardancy of the polylactic acid resin foam molded article obtained in the same manner as in Example 2 was evaluated except that the amount of the polyisocyanate compound added was 5 parts by weight.
（実施例６）
発泡剤をペンタンとしたこと以外は実施例２と同様にして得られたポリ乳酸系樹脂発泡成形体の難燃性の評価を行った。
(Example 6)
Except that pentane was used as the foaming agent, the flame retardancy of the polylactic acid resin foam molded article obtained in the same manner as in Example 2 was evaluated.
（比較例１）
アンモニウムポリホスフェートを添加しなかったこと以外は実施例１と同様にして得られたポリ乳酸系樹脂発泡成形体の難燃性の評価を行った。
(Comparative Example 1)
The flame retardancy of the polylactic acid resin foam molded article obtained in the same manner as in Example 1 was evaluated except that ammonium polyphosphate was not added.
（比較例２）
アンモニウムポリホスフェートを１重量部添加しこと以外は実施例１と同様にして得られたポリ乳酸系樹脂発泡成形体の難燃性の評価を行った。
(Comparative Example 2)
The flame retardancy of the polylactic acid resin foamed molding obtained in the same manner as in Example 1 was evaluated except that 1 part by weight of ammonium polyphosphate was added.
（比較例３）
アンモニウムポリホスフェートを１５重量部添加したこと以外は実施例１と同様にしたものの、良好な外観を有する発泡成形体は得られずその後の評価は不可能であった。
(Comparative Example 3)
Although it carried out similarly to Example 1 except having added 15 weight part of ammonium polyphosphate, the foaming molding which has a favorable external appearance was not obtained, and subsequent evaluation was impossible.
（比較例４）
乳酸成分の異性体比率（Ｌ体／Ｄ体）が９５／５であるポリ乳酸樹脂を使用したこと以外は実施例１と同様に発泡まで行ったものの、発泡粒子が得られずその後の評価は不可能であった。
(Comparative Example 4)
Except that a polylactic acid resin having an isomer ratio of lactic acid component (L-form / D-form) of 95/5 was used, foaming particles were not obtained, but the subsequent evaluation was performed in the same manner as in Example 1. It was impossible.
（比較例５）
ポリイソシアネート化合物の添加量を０．５重量部としたこと以外は実施例１と同様にしたものの、良好な外観を有する発泡成形体は得られずその後の評価は不可能であった。
(Comparative Example 5)
Except that the addition amount of the polyisocyanate compound was 0.5 parts by weight, the same procedure as in Example 1 was performed, but a foamed molded article having a good appearance was not obtained, and subsequent evaluation was impossible.
（比較例６）
発泡剤をヘキサンとしたこと以外は実施例１と同様にしたものの、良好な外観を有する発泡成形体は得られずその後の評価は不可能であった。
(Comparative Example 6)
Although it was carried out similarly to Example 1 except having used the foaming agent as hexane, the foaming molding which has a favorable external appearance was not obtained, and subsequent evaluation was impossible.
実施例１〜６及び比較例１〜６の各評価結果を表１に示す。 The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 6 are shown in Table 1.
Claims (5)
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| JP2005335545A JP2007138062A (en) | 2005-11-21 | 2005-11-21 | Polylactic acid-based resin composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009008262A1 (en) * | 2007-07-12 | 2009-01-15 | Fujifilm Corporation | Injection molded article of fiber-reinforced polylactic acid resin |
| WO2009119336A1 (en) * | 2008-03-25 | 2009-10-01 | 東レ株式会社 | Polylactic acid composition, and film comprising the same |
| CN102137728A (en) * | 2008-08-29 | 2011-07-27 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN101696319B (en) * | 2009-10-29 | 2011-11-16 | 同济大学 | Method for preparing microcapsule red phosphorus inflaming retarding polylactic acid |
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| WO1999021915A1 (en) * | 1997-10-29 | 1999-05-06 | Kanebo, Limited | Resin composition with biodegradability and foamability |
| JP2000017037A (en) * | 1998-06-30 | 2000-01-18 | Kanebo Ltd | Expandable resin composition having biodegadability |
| WO2005014706A1 (en) * | 2003-07-18 | 2005-02-17 | Ciba Specialty Chemicals Holding Inc. | Flame retardant polylactic acid |
| JP2005162804A (en) * | 2003-12-01 | 2005-06-23 | Toray Ind Inc | Polylactic acid-based resin composition and foam and manufacturing process of the foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09263651A (en) * | 1995-11-28 | 1997-10-07 | Dainippon Ink & Chem Inc | Foam and laminate |
| WO1999021915A1 (en) * | 1997-10-29 | 1999-05-06 | Kanebo, Limited | Resin composition with biodegradability and foamability |
| JP2000017037A (en) * | 1998-06-30 | 2000-01-18 | Kanebo Ltd | Expandable resin composition having biodegadability |
| WO2005014706A1 (en) * | 2003-07-18 | 2005-02-17 | Ciba Specialty Chemicals Holding Inc. | Flame retardant polylactic acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009008262A1 (en) * | 2007-07-12 | 2009-01-15 | Fujifilm Corporation | Injection molded article of fiber-reinforced polylactic acid resin |
| WO2009119336A1 (en) * | 2008-03-25 | 2009-10-01 | 東レ株式会社 | Polylactic acid composition, and film comprising the same |
| US8575254B2 (en) | 2008-03-25 | 2013-11-05 | Toray Industries, Inc. | Polylactic acid-based composition and film formed thereof |
| JP5560712B2 (en) * | 2008-03-25 | 2014-07-30 | 東レ株式会社 | Polylactic acid composition and film comprising the same |
| CN102137728A (en) * | 2008-08-29 | 2011-07-27 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN101696319B (en) * | 2009-10-29 | 2011-11-16 | 同济大学 | Method for preparing microcapsule red phosphorus inflaming retarding polylactic acid |
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