JP5062941B2 - Biodegradable resin injection molding method - Google Patents
Biodegradable resin injection molding method Download PDFInfo
- Publication number
- JP5062941B2 JP5062941B2 JP2003307631A JP2003307631A JP5062941B2 JP 5062941 B2 JP5062941 B2 JP 5062941B2 JP 2003307631 A JP2003307631 A JP 2003307631A JP 2003307631 A JP2003307631 A JP 2003307631A JP 5062941 B2 JP5062941 B2 JP 5062941B2
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- Prior art keywords
- temperature
- biodegradable resin
- resin
- mold
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006167 biodegradable resin Polymers 0.000 title claims description 46
- 238000001746 injection moulding Methods 0.000 title claims description 14
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 37
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- 238000002425 crystallisation Methods 0.000 claims description 30
- 230000008025 crystallization Effects 0.000 claims description 30
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- -1 polybutylene Polymers 0.000 claims description 10
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- 238000001816 cooling Methods 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
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- 239000002184 metal Substances 0.000 description 9
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- KIXKLKMUPZUMFB-UHFFFAOYSA-M potassium;2,3,4-trichlorobenzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=C(Cl)C(Cl)=C1Cl KIXKLKMUPZUMFB-UHFFFAOYSA-M 0.000 description 1
- HGJYOHAIVZXUML-UHFFFAOYSA-M potassium;3-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=CC=CC=2)=C1 HGJYOHAIVZXUML-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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- Injection Moulding Of Plastics Or The Like (AREA)
Description
本発明は、生分解性樹脂を使用する射出成形方法に係り、具体的には耐衝撃強度、耐熱温度を向上させ、成形品の加工を容易にするポリ乳酸樹脂の射出成形方法に関する。 The present invention relates to an injection molding method using a biodegradable resin, and more particularly to an injection molding method of a polylactic acid resin that improves impact strength and heat resistance temperature and facilitates processing of a molded product.
近年、ノートパソコン、携帯電話、PDA等の電子機器はモバイル化が進んでいる。これに伴い携帯電子機器の筐体は小型軽量化と、内蔵電子部品の発生熱に耐え得ること、衝突、落下等の衝撃に耐えることが要求されている。これら条件を満足させるために電子機器の筐体は軽金属材料と樹脂とを併用している。 In recent years, electronic devices such as notebook computers, mobile phones, and PDAs have been increasingly mobile. Along with this, the casing of portable electronic devices is required to be small and light, to withstand the heat generated by built-in electronic components, and to withstand impacts such as collision and dropping. In order to satisfy these conditions, the housing of the electronic device uses a light metal material and a resin together.
一方、地球環境に優しい製品、つまりリサイクルの可能な製品、製造方法が検討されている。このために軽金属や樹脂に代わって生分解性樹脂が使用され始めた。この生分解性樹脂としてポリ乳酸が適用されている。このポリ乳酸を主成分とした筐体は微生物によって大略、水と二酸化炭素とに分解される。結果としてポリ乳酸を主成分とする樹脂はリサイクルに適当な製品である。 On the other hand, products that are friendly to the global environment, that is, recyclable products and manufacturing methods are being studied. For this reason, biodegradable resins have begun to be used in place of light metals and resins. Polylactic acid is applied as this biodegradable resin. The casing mainly composed of polylactic acid is roughly decomposed into water and carbon dioxide by microorganisms. As a result, a resin based on polylactic acid is a product suitable for recycling.
図2はポリ乳酸樹脂から成る筐体の正面面である。
この樹脂筐体は大略長さ約265mm、縦約10mm、横幅約175mm、板厚約0.8mmである。この筐体は一般的に射出成形方法によって作られる。具体的には射出成形機の金型のキャビティー内に加熱溶融したポリ乳酸樹脂を射出し、キャビティー内にポリ乳酸樹脂を満たし、そしてポリ乳酸樹脂を個化する。続いて個化されたポリ乳酸樹脂を前記キャビティー内から離型し成形品となる。つまり金型温度はポリ乳酸樹脂の射出から成形品を離型する迄は金型を一定温度の例えば20度C〜40度Cの低温で変化させないで製造されている。
FIG. 2 is a front view of a housing made of polylactic acid resin.
This resin casing is approximately 265 mm long, approximately 10 mm long, approximately 175 mm wide, and approximately 0.8 mm thick. This housing is generally made by an injection molding method. Specifically, the polylactic acid resin heated and melted is injected into the cavity of the mold of the injection molding machine, the polylactic acid resin is filled into the cavity, and the polylactic acid resin is individualized. Subsequently, the individualized polylactic acid resin is released from the cavity to form a molded product. That is, the mold temperature is manufactured without changing the mold at a constant temperature, for example, 20 degrees C to 40 degrees C, until the molded product is released from the injection of the polylactic acid resin.
しかし、このポリ乳酸樹脂で作られた筐体は仕様条件の耐衝撃強度、耐熱温度より低い。このために耐衝撃強度と耐熱温度を向上する必要がある。 However, the casing made of this polylactic acid resin is lower than the impact resistance strength and heat resistance temperature of the specified conditions. For this reason, it is necessary to improve impact strength and heat resistance temperature.
これらの耐衝撃強度と耐熱温度とは生分解性樹脂の結晶化を促進することで向上する。結晶化を促進する具体的な1つの技術として下記特許文献1に記載された技術がある。特許文献1に開示されている成形方法は結晶化を促進するするために、生分解性樹脂に結晶核剤のタルク、シリカ、乳酸カルシューム等の粉末を添加している。
しかしながら、上記特許文献1では成形品が脆くなる。さらに成形品の表面にひけが発生する。このため筐体に不適当である。次に上記特許文献2ではアニール処理に多くの時間を要し量産に不適当であり、且つアニール処理中に成形品が変形する。更に、前述したような金型を20度C〜40度Cの低温に一定保持した射出成形方法ではポリ乳酸の結晶化が遅く多くの時間を必要とする。このために結晶化を促進する温度例えば90〜110度Cの一定温度にて行なうと成形品の冷却に多くの時間を要する。またガラス転移温度以上の場合は結晶化部分と非結晶化の部分の内、特に結晶部分が結晶化して終わった時にでも非結晶化の部分が軟化し柔らかい。このために成形品を金型から離型する時に変形し、且つ製品の端面にバリが生じ、さらに製品の表面にひけが生じ不良品になる。このために成形品に生じたバリを切除する処理が必要となり、さらに成形品に生じたひけにより歩留りが低下する。 However, in the said patent document 1, a molded article becomes weak. Furthermore, sink marks occur on the surface of the molded product. For this reason, it is unsuitable for a housing. Next, in Patent Document 2, it takes a long time for the annealing process and is unsuitable for mass production, and the molded product is deformed during the annealing process. Further, in the injection molding method in which the mold as described above is kept constant at a low temperature of 20 ° C. to 40 ° C., the crystallization of polylactic acid is slow and requires a lot of time. For this reason, if it is performed at a temperature for promoting crystallization, for example, a constant temperature of 90 to 110 ° C., it takes a long time to cool the molded product. When the temperature is higher than the glass transition temperature, the crystallized portion and the noncrystallized portion, especially when the crystal portion is crystallized, the noncrystallized portion is softened and soft. For this reason, the molded product is deformed when released from the mold, and burrs are generated on the end surface of the product, and sink marks are formed on the surface of the product, resulting in a defective product. For this reason, it is necessary to remove the burrs generated in the molded product, and the yield decreases due to sink marks generated in the molded product.
本発明の目的はポリ乳酸から成る成形品の耐衝撃強度、耐熱温度を向上し、更に成形品が脆くなく、そして成形品が変形することなく、更に処理時間を多く要せず、歩留りを向上して量産に最適な生分解性樹脂の製造方法を提供する。 The object of the present invention is to improve the impact resistance strength and heat resistance temperature of molded products made of polylactic acid, and the molded products are not brittle, the molded products are not deformed, and further processing time is not required and the yield is improved. Thus, a method for producing a biodegradable resin optimal for mass production is provided.
本発明は金型内に生分解性樹脂を射出した後に、前記生分解性樹脂を冷却固化する射出成形方法において、前記生分解性樹脂をガラス転移温度以上、且つ生分解性樹脂の結晶化最大速度の温度未満の前記金型のキャビティ内に射出する工程と、その後に前記生分解性樹脂を結晶化させるために生分解性樹脂の結晶化最大速度の温度から±10度Cで所定時間保持する工程と、続いて前記生分解性樹脂をガラス転移温度から10度C以上低い温度以下にて離型する工程とを有する生分解性樹脂の射出成形方法である。 The present invention relates to an injection molding method in which the biodegradable resin is cooled and solidified after the biodegradable resin is injected into a mold, and the biodegradable resin has a glass transition temperature or higher and the biodegradable resin has a maximum crystallization. A step of injecting into the mold cavity below the temperature of the speed, and then maintaining the temperature within ± 10 degrees C for a predetermined time from the temperature of the maximum speed of crystallization of the biodegradable resin in order to crystallize the biodegradable resin And a step of releasing the biodegradable resin at a temperature lower than or equal to 10 ° C. from the glass transition temperature.
上記のようにガラス転移温度以上、且つポリ乳酸の結晶化最大速度の温度未満の金型に生分解性樹脂を射出するために成形品にばりを発生しない。さらに生分解性樹脂をポリ乳酸の結晶化最大速度の温度から±10度Cで所定の結晶化時間保持するために生分解性樹脂の結晶化を促進できる。その上生分解性樹脂をガラス転移温度から10度C以上低い温度に冷却する。このために金型から成形品を離型する時に形状変形が無い。 As described above, since the biodegradable resin is injected into the mold having a temperature equal to or higher than the glass transition temperature and lower than the temperature of the maximum crystallization rate of polylactic acid, no flash is generated on the molded product. Furthermore, since the biodegradable resin is maintained at a predetermined crystallization time at ± 10 ° C. from the maximum crystallization temperature of polylactic acid, crystallization of the biodegradable resin can be promoted. In addition, the biodegradable resin is cooled to a temperature lower by 10 ° C. or more from the glass transition temperature. For this reason, there is no shape deformation when the molded product is released from the mold.
本発明の実施の形態を説明する。 An embodiment of the present invention will be described.
次に、本発明を実施例に基づき具体的に説明する。 Next, the present invention will be specifically described based on examples.
最初に成形材料である生分解性樹脂組成物を調製する。
<生分解性樹脂の調製>
ポリ乳酸(三井化学株製 商品名;レイシアH−100J)と、ポリブレンサクシネート(昭和高分子株製 商品名;ビオノーレ1020)とを使用した。
First, a biodegradable resin composition that is a molding material is prepared.
<Preparation of biodegradable resin>
Polylactic acid (trade name; Lacia H-100J, manufactured by Mitsui Chemicals, Inc.) and polybrene succinate (trade name, manufactured by Showa Polymer Co., Ltd .; Bionore 1020) were used.
上記ポリ乳酸90%wtとポリブレンサクシネート10%wtとを混練機を使用して生分解性樹脂を作成した。混練機は日本製鋼所株 商品名;TEX30 αを使用した。製造条件はシリンダー温度180度C、スクリュー回転数150rpmである。この混練された樹脂を射出成形機(FANUC株製 製品名α−300B)を使用して下記の製造条件で試料1〜8を作成した。この射出成形機の成形条件はシリンダー温度180度C、射出速度25mm/秒、保圧1800Kg/cmである。この射出成形機の金型温度制御はシスコ株製の昇温簡易型ボイラとバルブユニットから構成されたシステムを使用した。昇温速度は約2.8度C/秒、降温速度は約1.5度C/秒である。この金型のキャビティ内壁にSi02の無機膜を設けている。この無機膜を設けることで金型のキャビティ内壁の温度を均一にすることができる。この無機膜はスプレーを使用してSi02を噴霧することで行なわれる。SiO2以外にTiAlN、フッ素、PBI(ポリベンゾイミダゾール)等の内、少なくとも1つを使用できる。 A biodegradable resin was prepared using a kneader between the polylactic acid 90% wt and the polybrene succinate 10% wt. As the kneading machine, Nippon Steel Works Co., Ltd. trade name; TEX30α was used. The manufacturing conditions are a cylinder temperature of 180 ° C. and a screw rotation speed of 150 rpm. Samples 1 to 8 were prepared from the kneaded resin using an injection molding machine (product name α-300B, manufactured by FANUC Corporation) under the following production conditions. The molding conditions of this injection molding machine are a cylinder temperature of 180 ° C., an injection speed of 25 mm / second, and a holding pressure of 1800 Kg / cm. The mold temperature control of this injection molding machine used a system made up of a temperature rising simple boiler and valve unit made by Cisco. The temperature increase rate is about 2.8 degrees C / second, and the temperature decrease rate is about 1.5 degrees C / second. An Si02 inorganic film is provided on the cavity inner wall of the mold. By providing this inorganic film, the temperature of the inner wall of the cavity of the mold can be made uniform. This inorganic film is formed by spraying Si02 using a spray. In addition to SiO2, at least one of TiAlN, fluorine, PBI (polybenzimidazole) and the like can be used.
次に各試料の製造について説明する。
<試料の製造条件>
図1は試料を作成する金型又はポリ乳酸樹脂の温度サイクルを示す図である。図1中のT2はポリ乳酸樹脂を射出する時の金型温度(度C)、Tmaxはポリ乳酸樹脂を結晶化させる温度(度C)、S1は温度保持時間(秒)、S2は結晶化工程時間(秒)、Tminは試料を金型型から離型する温度(度C)である。 金型温度の初期温度は約30度Cである。この金型は2.8度C/秒の昇温速度で加熱される。金型温度がT2度Cになった時にポリ乳酸樹脂が混練機から金型内つまりキャビティに射出される。そしてポリ乳酸樹脂がTmax温度度CでS1時間保持される。所定時間経過後、1.5度C/秒の降温速度で冷却される。降温途中のTmin温度Cで冷却個化された試料を金型から離型する。従って樹脂は結晶化時間S2の期間内で結晶化される。この温度サイクルで成形品が繰り返し作られる。
Next, the production of each sample will be described.
<Sample manufacturing conditions>
FIG. 1 is a diagram showing a temperature cycle of a mold for producing a sample or a polylactic acid resin. In FIG. 1, T2 is a mold temperature (degree C) when injecting the polylactic acid resin, Tmax is a temperature for crystallization of the polylactic acid resin (degree C), S1 is a temperature holding time (second), and S2 is crystallization. The process time (seconds) and Tmin are temperatures (degrees C) at which the sample is released from the mold. The initial temperature of the mold temperature is about 30 degrees C. This mold is heated at a rate of temperature increase of 2.8 degrees C / sec. When the mold temperature reaches T2 degrees C, the polylactic acid resin is injected from the kneader into the mold, that is, into the cavity. The polylactic acid resin is held at the Tmax temperature degree C for S1 time. After a predetermined time elapses, cooling is performed at a temperature lowering rate of 1.5 degrees C / second. The sample that has been cooled and cooled at the Tmin temperature C during the temperature reduction is released from the mold. Therefore, the resin is crystallized within the period of the crystallization time S2. The molded product is repeatedly made in this temperature cycle.
各試料の具体的な各試料の製造条件は後述の通りである。
・試料1の製造条件はT2が60度C、Tmaxが100度C、S1が0秒、S2が64秒、Tminが30度Cである。
・試料2の製造条件はT2;60度C、Tmax;100度C、S1が60秒、S2;124秒、Tmin;30度Cである。
・試料3の製造条件はT2;60度C、Tmax;100度C、S1が120秒、S2;184秒、Tmin;30度Cである。
・試料4の製造条件はT2;40度C、Tmax;100度C、S1が60秒、S2;131秒、Tmin;30度Cである。つまり試料4の製造条件はポリ乳酸樹脂が射出される時の金型温度が40度Cであり、ポリ乳酸樹脂のガラス転移温度60〜100度Cより低い。
・試料5の製造条件はT2;100度C、Tmax;100度C、S1が60秒、S2;110秒、Tmin;30度Cである。
・試料6の製造条件はT2;60度C、Tmax;130度C、S1が60秒、S2;162秒、Tmin;30度Cである。つまり試料6の製造条件は試料を結晶化させる温度Tmaxが130度Cであり、ポリ乳酸の結晶化速度が最も早い90〜110度Cをこえている。
・試料7の製造条件はT2;30度C、Tmax;30度C、S1が0秒、S2;68秒、Tmin;30度Cである。つまり試料7の製造条件はポリ乳酸樹脂が射出される時の金型温度T2と試料を結晶化させる温度金型温度Tmaxと試料を金型から離型する温度Tminとが常に30度C一定に保たれている。換言すると従来技術で説明した一般慣用技術である。
・試料8の製造条件はT2;100度C、Tmax;100度C、S1が0秒、S2;208秒、Tmin;100度Cである。つまり試料8の製造条件は試料が射出される時の金型温度T2と試料を結晶化させる温度金型温度Tmaxと試料を金型から離型する温度Tminとが常時100度C一定に保たれている。
<試料の評価>
各試料の評価は結晶化度(DSC)、衝撃強度、耐熱温度と成形品のバリ、ひけ、変形について行なった。
(1)結晶化度(DSC)は示差走査熱量測定機(セイコー電子株製 商品名DSC100)を用いて測定した。上記示差走査熱量測定機は下記の算術にて求められる 結晶化度(DSC)%=(ΔHm−ΔHcc)÷ΔHm
(ただし、ΔHm;結晶融解ピーク熱量 ΔHcc;昇温時結晶化ピーク熱量である。)この結晶化度(DSC)%は数値が大きい程、結晶化されていることを示し、小さい程、結晶化されていないことを示す。
(2)衝撃強度の測定はアイゾット衝撃強度の測定により行なった。具体的には、アイゾット衝撃試験機(東洋精機株製 商品名:B−121202403)を使用し、JIS7110に準拠してアイゾット衝撃試験を行った。
(3)耐熱温度の評価は荷重たわみ温度 ISO75試験にて行なった。具体的には、荷重たわみ温度の試験用試験片(長さ80mm×幅10mm×厚さ4mm)を作成し、伝熱可能な液体中に試験片の支点間距離が64mmとなるように両端を固定した。そして試験片の中央部分に曲げ応力1.80MPaを負荷し昇温速度120度C/hrで前記液体を加熱して、試験片の中央部分が0.32mmのたわみ量になった時の温度を測定し評価する。
(4)成形品のバリ、ひけと変形の評価は具体的には目視にて行った。バリとは押圧される互いの金型の隙間に入り込む樹脂が成形品に形成されるものであり、成形品の端面に0.1mm以上の不要物が発見された場合にバリ有りと評価した。次に、ひけは成形品の表面に発生する窪みであり、目視可能な例えば深さ0.1mm以上をひけ有りと評価した。続いて変形の評価は成形品の外形状が内側または外側に0.1mm以上変形している場合に変形ありとした。
The specific production conditions for each sample are as described below.
The manufacturing conditions of sample 1 are T2 of 60 degrees C, Tmax of 100 degrees C, S1 of 0 seconds, S2 of 64 seconds, and Tmin of 30 degrees C.
The production conditions of Sample 2 are T2; 60 degrees C, Tmax; 100 degrees C, S1 is 60 seconds, S2: 124 seconds, Tmin: 30 degrees C.
-The manufacturing conditions of the sample 3 are T2; 60 degree C, Tmax; 100 degree C, S1 for 120 seconds, S2; 184 seconds, Tmin;
-The manufacturing conditions of the sample 4 are T2; 40 degree C, Tmax; 100 degree C, S1 for 60 seconds, S2; 131 seconds, Tmin; That is, the manufacturing condition of the sample 4 is that the mold temperature when the polylactic acid resin is injected is 40 ° C., which is lower than the glass transition temperature of the polylactic acid resin of 60 to 100 ° C.
-The manufacturing conditions of the sample 5 are T2; 100 degree C, Tmax; 100 degree C, S1 for 60 seconds, S2; 110 seconds, Tmin; 30 degree C.
-The manufacturing conditions of the sample 6 are T2; 60 degree C, Tmax; 130 degree C, S1 for 60 seconds, S2; 162 seconds, Tmin; 30 degrees C. That is, the manufacturing conditions of the sample 6 are that the temperature Tmax for crystallizing the sample is 130 ° C., and the crystallization speed of polylactic acid exceeds 90 to 110 ° C.
-The manufacturing conditions of the sample 7 are T2; 30 degree C, Tmax; 30 degree C, S1 is 0 second, S2: 68 second, Tmin; 30 degree C. That is, the manufacturing condition of the sample 7 is that the mold temperature T2 when the polylactic acid resin is injected, the temperature mold temperature Tmax for crystallizing the sample, and the temperature Tmin for releasing the sample from the mold are always constant at 30 degrees C. It is kept. In other words, it is the general conventional technique described in the prior art.
-The manufacturing conditions of the sample 8 are T2; 100 degree C, Tmax; 100 degree C, S1 is 0 second, S2: 208 second, Tmin; 100 degree C. In other words, the manufacturing condition of the sample 8 is that the mold temperature T2 when the sample is injected, the temperature mold temperature Tmax for crystallizing the sample, and the temperature Tmin for releasing the sample from the mold are always kept constant at 100 degrees C. ing.
<Evaluation of sample>
Each sample was evaluated for crystallinity (DSC), impact strength, heat resistance temperature, burrs, sink marks and deformation of the molded product.
(1) Crystallinity (DSC) was measured using a differential scanning calorimeter (trade name DSC100, manufactured by Seiko Denshi Co., Ltd.). The differential scanning calorimeter is obtained by the following arithmetic: Crystallinity (DSC)% = (ΔHm−ΔHcc) ÷ ΔHm
(However, ΔHm; Crystal melting peak calorific value ΔHcc: Crystallization peak calorific value at the time of temperature rise.) The larger the numerical value (DSC)%, the more crystallized, the smaller the crystallizing. Indicates that it has not been.
(2) Impact strength was measured by measuring Izod impact strength. Specifically, using an Izod impact tester (trade name: B-121202403, manufactured by Toyo Seiki Co., Ltd.), an Izod impact test was performed in accordance with JIS 7110.
(3) Evaluation of heat-resistant temperature was performed by load deflection temperature ISO75 test. Specifically, a test specimen (length 80 mm × width 10 mm × thickness 4 mm) having a deflection temperature under load is prepared, and both ends are set so that the distance between fulcrums of the specimen is 64 mm in a heat transferable liquid. Fixed. Then, a bending stress of 1.80 MPa is applied to the central portion of the test piece, and the liquid is heated at a heating rate of 120 ° C./hr, and the temperature when the central portion of the test piece has a deflection of 0.32 mm is set. Measure and evaluate.
(4) The evaluation of burrs, sink marks and deformation of the molded product was performed visually. The burr is a resin in which a resin entering the gap between the pressed molds is formed in the molded product. When an unnecessary object of 0.1 mm or more is found on the end surface of the molded product, it is evaluated that there is a burr. Next, sink marks are depressions generated on the surface of the molded product, and a visible depth of, for example, 0.1 mm or more was evaluated as having sink marks. Subsequently, the deformation was evaluated when the outer shape of the molded product was deformed by 0.1 mm or more inward or outward.
上記各評価を試料1〜8について行なった。各評価の結果を表1に表記している。 Each said evaluation was performed about the samples 1-8. The results of each evaluation are shown in Table 1.
試料1は温度保持時間S1が0(秒),結晶化工程時間S2が64(秒)であるために結晶化が58%であり、結晶化度が低い。このためアイゾット衝撃強度が低く7.8(Kgf・cm/ 平方cm) である。耐熱温度は低く60度Cである。そしてバリ、ひけ、変形は無い。
試料2、3、5は結晶化が100%であり、バリ、ひけ、変形は無い。
試料4は結晶化が100%である。しかしT2がガラス転移温度以下のために、射出時に樹脂の表層面が個化された後、再溶融されながら流入する。この時に金型内圧力が増し、金型相互の隙間に樹脂が入り込みバリが発生した。
Since sample 1 has a temperature holding time S1 of 0 (seconds) and a crystallization process time S2 of 64 (seconds), the crystallization is 58% and the crystallinity is low. Therefore, the Izod impact strength is low, 7.8 (Kgf · cm / square cm). The heat-resistant temperature is as low as 60 degrees C. And there are no burr, sink, and deformation.
Samples 2, 3, and 5 are 100% crystallized and have no burrs, sink marks, or deformation.
Sample 4 has 100% crystallization. However, since T2 is equal to or lower than the glass transition temperature, the resin surface layer is individualized at the time of injection, and then flows in while being remelted. At this time, the pressure inside the mold increased, and the resin entered the gap between the molds to generate burrs.
試料6は結晶化が100%である。しかしTmaxが結晶化最大速度の温度以上のために、樹脂の粘度が低くなり、流動し易く金型相互の隙間に進入してバリが発生した。さらに成形品の表面が高温であり、この高温のために成形品の表面温度が不均一になり、ひけが発生したと思われる。そしてガラス転移温度以上にて成形品を離型したために押出ピンの押圧によって成形品が変形した。 Sample 6 has 100% crystallization. However, since Tmax is equal to or higher than the temperature of the maximum crystallization speed, the viscosity of the resin is low, and the resin easily flows and enters the gaps between the molds to generate burrs. Further, the surface of the molded product is high temperature, and the surface temperature of the molded product becomes non-uniform due to this high temperature, which seems to have caused sink marks. And since the molded product was released above the glass transition temperature, the molded product was deformed by pressing the extrusion pin.
試料7はT2の温度が30度C一定であり、結晶化工程時間S2が短時間の68(秒)である。このために結晶化が低く38%である。このためアイゾット衝撃強度が低く7.8(Kgf・cm/ 平方cm) である。耐熱温度は低く60度Cである。また成形品の表面がガラス転移温度以下の低温であり、成形品の表面の一部が収縮して表面が不均一の状態で個化されてひけを発生した。 In the sample 7, the temperature of T2 is constant at 30 ° C., and the crystallization process time S2 is 68 (seconds), which is a short time. For this reason, crystallization is low and is 38%. Therefore, the Izod impact strength is low, 7.8 (Kgf · cm / square cm). The heat-resistant temperature is as low as 60 degrees C. Further, the surface of the molded product was a low temperature below the glass transition temperature, and a part of the surface of the molded product contracted, and the surface was individualized in a non-uniform state to generate sink marks.
試料8は温度が100度C一定であり、ポリ乳酸樹脂は個化されなかった。このために成形品を離型する時に変形し、成形品の全端面にバリが発生した。従ってアイゾット衝撃強度、耐熱温度測定が出来なかった。 Sample 8 had a constant temperature of 100 ° C., and the polylactic acid resin was not individualized. For this reason, the molded product was deformed when it was released, and burrs were generated on the entire end surface of the molded product. Therefore, Izod impact strength and heat resistant temperature could not be measured.
結果として生分解性樹脂を主成分とする成形体の製造方法はポリ乳酸樹脂をガラス転移温度以上、且つポリ乳酸の結晶化最大速度の温度未満の金型に射出し、ポリ乳酸の結晶化最大速度の温度で所定時間だけ保持し樹脂を結晶化させた後に、ガラス転移温度から40度C以上低い温度に冷却して成形品を金型から離型すると良い。 As a result, the method for producing a molded product mainly composed of a biodegradable resin injects polylactic acid resin into a mold having a temperature higher than the glass transition temperature and lower than the maximum crystallization speed of polylactic acid, thereby maximizing crystallization of polylactic acid. After the resin is crystallized by holding at the speed temperature for a predetermined time, the molded product is preferably released from the mold by cooling to a temperature lower than the glass transition temperature by 40 ° C. or more.
上記生分解性樹脂はポリ乳酸とポリカプロラクトンとの混合以外に、ポリ乳酸、ポリヒドロキシブチレート、ポリブレンサクシネートの少なくとも1つから構成されても同様な効果が得られる。 Similar effects can be obtained when the biodegradable resin is composed of at least one of polylactic acid, polyhydroxybutyrate, and polybrene succinate in addition to the mixture of polylactic acid and polycaprolactone.
上記生分解性樹脂組成物には、さらにシリコーン系難燃剤、有機金属塩系難燃剤、有機リン系難燃剤、金属酸化物系難燃剤、金属水酸化物系難燃剤等を添加することができる。これにより難燃性が向上して延焼が抑制でき、生分解性樹脂組成物の流動性が向上して成形性を良好にできる。 Silicone flame retardants, organometallic salt flame retardants, organophosphorous flame retardants, metal oxide flame retardants, metal hydroxide flame retardants, and the like can be further added to the biodegradable resin composition. . Thereby, a flame retardance improves and a fire spread can be suppressed, the fluidity | liquidity of a biodegradable resin composition improves, and a moldability can be made favorable.
上記シリコーン系難燃剤は、例えばアルキルシロキサン(信越シリコーン株 商品名“X40−9805”)、アルキルフェニルシロキサン(ダウコーニング・シリコーン社 商品名“MB50−315”)等を使用できる。 Examples of the silicone-based flame retardant include alkyl siloxane (trade name “X40-9805” manufactured by Shin-Etsu Silicone Co., Ltd.) and alkyl phenyl siloxane (trade name “MB50-315” manufactured by Dow Corning Silicone Co., Ltd.).
上記有機金属塩系難燃剤としては、具体的にはトリクロロベンゼンスルフォン酸カリウム、パーフルオロブタンスルフォン酸カリウム、ジフェニルスルフォン−3−スルフォン酸カリウム等の有機スルフォン酸金属塩、芳香族スルフォンイミド金属塩、あるいはスチレン系重合体、ポリフェニレンエーテル等の芳香族基含有重合体の芳香環に、スルフォン酸金属塩、硫酸金属塩、リン酸金属塩、ホウ酸金属塩が結合したポリスチレンスルフォン酸アルカリ金属塩等を使用できる。 上記有機リン系難燃剤としては、例えば、ホスフィン、ホスフィンオキシド、ビホスフィン、ホスホニウム塩、ホスフィン酸塩、リン酸エステル、亜リン酸エステル等を用いることができる。より具体的には、トリフェニルフォスフェート、メチルネオペンチルフォスファイト、ペンタエリスリトールジエチルジフォスファイト、メチルネオペンチルフォスフォネート、フェニルネオペンチルフォスフェート、ペンタエリスリトールジフェニルジフォスフェート、ジシクロペンチルハイポジフォスフェート、ジネオペンチルハイポフォスファイト、フェニルピロカテコールフォスファイト、エチルピロカテコールフォスフェート、ジピロカテコールハイポジフォスフェート等を使用できる。 Specific examples of the organic metal salt flame retardant include organic sulfonic acid metal salts such as potassium trichlorobenzene sulfonate, potassium perfluorobutane sulfonate, potassium diphenylsulfone-3-sulfonate, aromatic sulfonic imide metal salts, Alternatively, a polystyrene sulfonate alkali metal salt in which a sulfonic acid metal salt, a sulfate metal salt, a phosphate metal salt, or a borate metal salt is bonded to an aromatic ring of an aromatic group-containing polymer such as a styrene polymer or polyphenylene ether. Can be used. Examples of the organic phosphorus flame retardant include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate ester, phosphite ester, and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl high positive phosphate, Dineopentyl hypophosphite, phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate, dipyrrocatechol high positive phosphate and the like can be used.
上記金属酸化物系難燃剤としては例えば酸化マグネシウム等が使用できる。上記金属水酸化物系難燃剤としては例えば水酸化マグネシウム等が使用できる。 As said metal oxide type flame retardant, magnesium oxide etc. can be used, for example. As the metal hydroxide flame retardant, for example, magnesium hydroxide can be used.
上記生分解性樹脂組成物には、さらに改質剤として乳酸系ポリエステルを添加することができる。これにより耐衝撃性が向上するのみならず、難燃化効果も向上する。この乳酸系ポリエステルとしては乳酸とジカルボン酸とジオールとを共重合したポリマーが使用できる。このジカルボン酸としては例えば、コハク酸、アジピン酸、セバシン酸、デカンジカルボン酸、シクロヘキサンジカルボン酸、フタル酸、テレフタル酸、イソフタル酸等を使用できる。また、ジオールとしては、例えば、エチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール等を挙げることができる。乳酸系ポリエステルは例えば大日本インキ株社製 商品名;EXP−PD−150を使用できる。さらに他の改質剤としては、セバシン酸1,3−ブタンジオール等を使用できる。 The biodegradable resin composition may further contain a lactic acid polyester as a modifier. This not only improves impact resistance, but also improves the flame retardant effect. As the lactic acid-based polyester, a polymer obtained by copolymerizing lactic acid, dicarboxylic acid and diol can be used. Examples of the dicarboxylic acid include succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, and isophthalic acid. Examples of the diol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like. As the lactic acid-based polyester, for example, trade name: EXP-PD-150 manufactured by Dainippon Ink Co., Ltd. can be used. Further, as other modifiers, 1,3-butanediol sebacate and the like can be used.
上記生分解性樹脂組成物には、さらに充填剤としてマイカ、モンモリロナイト、カオリン等を添加することができる。 Mica, montmorillonite, kaolin and the like can be further added to the biodegradable resin composition as a filler.
上記生分解性樹脂組成物には、さらに充填剤として麻繊維、キチン・キトサン、椰子殻繊維、ケナフ、これらから誘導された短繊維、これらから誘導された粉体等を添加することができる。これにより、成形体の剛性および耐熱性を向上できる。また、これらは天然素材であり成形体の生分解性を低下させない。 The biodegradable resin composition may further contain hemp fibers, chitin / chitosan, coconut shell fibers, kenaf, short fibers derived therefrom, powders derived therefrom, and the like as fillers. Thereby, the rigidity and heat resistance of a molded object can be improved. These are natural materials and do not deteriorate the biodegradability of the molded body.
上記生分解性樹脂組成物には、さらに充填剤として、ガラス繊維、カーボン繊維、ガラスフレーク、ガラスビーズ、セラミックビーズ、アスベスト、ワラステナイト、クレー、マイカ、セリサイト、ゼオライト、ベントナイト、モンモリロナイト、合成マイカ、ドロマイト、カオリン、微粉ケイ酸、長石粉、チタン酸カリウム、シラスバルーン、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、酸化カルシウム、酸化アルミニウム、酸化チタン、ケイ酸アルミニウム、酸化ケイ素、石膏、ノバキュライト、ドーソナイトまたは白土など等を添加することが好ましい。これにより成形体の剛性を大きくできる。また、上記充填剤は、ポリ乳酸や脂肪酸等でコーティング等の表面処理がされていてもよいし、シランカップリング剤等で表面処理がされていてもよい。 The biodegradable resin composition further contains, as a filler, glass fiber, carbon fiber, glass flake, glass bead, ceramic bead, asbestos, wollastonite, clay, mica, sericite, zeolite, bentonite, montmorillonite, synthetic mica. , Dolomite, kaolin, fine powdered silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, Novaclite, dosonite or It is preferable to add clay or the like. Thereby, the rigidity of a molded object can be enlarged. The filler may be subjected to surface treatment such as coating with polylactic acid or fatty acid, or may be surface treated with a silane coupling agent or the like.
上記生分解性樹脂組成物には、必要に応じて他の添加剤を含ませることができる。例えば樹脂の加水分解を抑制可能な物質として、カルボジイミド化合物、イソシアネート化合物、オキサゾリン系化合物等を添加することができる。また、乳酸系以外のポリエステルやポリエーテル等の可塑剤を必要に応じて添加して使用することもできる。さらに、耐候性改良剤、酸化防止剤、熱安定剤(ヒンダードフェノール、ヒドロキノン、ホスファイト類およびこれらの置換体等)、紫外線吸収剤(レゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノン等)、滑剤(グラファイト、フッ素樹脂など)、離型剤(モンタン酸およびその塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミドおよびポリエチレンワックス等)、着色剤(ニグロシンから成る染料および硫化カドミウム、フタロシアニンから成る顔料)着色防止剤(亜リン酸塩、次亜リン酸塩など)、相溶化剤などを配合することも可能である。これらの混練により、耐熱性、曲げ強度、衝撃強度、難燃性等も改善される。これらの材料を混合された生分解性樹脂は本製造方法を使用することによってノートパソコン、携帯電話等を代表とする電子機器用筐体等の成形体への適用が最適になる。 The biodegradable resin composition may contain other additives as necessary. For example, a carbodiimide compound, an isocyanate compound, an oxazoline compound, or the like can be added as a substance capable of suppressing the hydrolysis of the resin. Moreover, plasticizers, such as polyester and polyether other than lactic acid type, can also be added and used as needed. Furthermore, weather resistance improvers, antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitutes), ultraviolet absorbers (resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants (graphite) , Fluororesins, etc.), mold release agents (montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide and polyethylene wax, etc.), coloring agents (dyes comprising nigrosine and pigments comprising cadmium sulfide and phthalocyanine) An inhibitor (phosphite, hypophosphite, etc.), a compatibilizing agent and the like can be blended. These kneadings improve heat resistance, bending strength, impact strength, flame retardancy, and the like. The biodegradable resin mixed with these materials is optimally applied to a molded body such as a casing for an electronic device typified by a notebook personal computer or a mobile phone by using this manufacturing method.
本発明の生分解性樹脂を主成分とする成形体の製造方法はポリ乳酸から成る成形品の耐衝撃強度、耐熱温度を向上し、更に成形品が脆くなく、そして成形品が変形することなく、更に処理時間を多く要せず、歩留りを向上して量産に最適な生分解性樹脂の製造方法を提供することができる。 The method for producing a molded article mainly composed of the biodegradable resin of the present invention improves the impact strength and heat resistance temperature of a molded article made of polylactic acid, and the molded article is not brittle and the molded article is not deformed. In addition, it is possible to provide a method for producing a biodegradable resin that is optimal for mass production by improving the yield without requiring much processing time.
T2;試料を金型に射出する温度(度C)、
Tmax;試料を結晶化させる温度(度C)、
S2;結晶化工程時間(秒)、
Tmin;試料を金型型から離型する温度(度C)である。
T2: temperature at which the sample is injected into the mold (degree C),
Tmax: temperature at which the sample is crystallized (degree C),
S2: crystallization process time (seconds),
Tmin: temperature (degree C) at which the sample is released from the mold.
Claims (3)
前記生分解性樹脂をガラス転移温度以上、且つ前記生分解性樹脂の結晶化最大速度の温度未満である第1の温度の前記金型のキャビティ内に射出する工程と、
その後に前記生分解性樹脂を結晶化させるために、前記生分解性樹脂の結晶化最大速度の温度から±10度Cの温度範囲にあり、且つ前記第1の温度よりも高い第2の温度で所定時間保持する工程と、
続いて前記生分解性樹脂をガラス転移温度から10度C以上低い温度以下にて離型する工程と、を有することを特徴とする生分解性樹脂の射出成形方法。 In the injection molding method of cooling and solidifying the biodegradable resin after injecting the biodegradable resin into the mold,
The biodegradable resin glass transition temperature or higher, a step of injecting the first of said mold cavity temperature is and crystallization below the maximum speed of the temperature of the biodegradable resin,
To subsequently crystallizing the biodegradable resin, there the temperature of the crystallization the maximum speed of the biodegradable resin to a temperature range of ± 10 ° C, and the second is higher than the first temperature second temperature And holding for a predetermined time in
Then injection molding method of the biodegradable resin, characterized in that and a step of releasing at 10 ° C or more lower temperature below the biodegradable resin from the glass transition temperature.
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