JPH1112379A - Biodegradable resin foam - Google Patents
Biodegradable resin foamInfo
- Publication number
- JPH1112379A JPH1112379A JP9207049A JP20704997A JPH1112379A JP H1112379 A JPH1112379 A JP H1112379A JP 9207049 A JP9207049 A JP 9207049A JP 20704997 A JP20704997 A JP 20704997A JP H1112379 A JPH1112379 A JP H1112379A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- pts
- long
- chain fatty
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は耐湿性を有する生分
解樹脂発泡体に関するものである。従来、発泡ポリスチ
レンのような樹脂発泡体は、生鮮食料品のトレーやカッ
プ麺の容器や家電製品等の緩衝材として使用されてき
た。しかし、ポリスチレンのような合成樹脂製品は、使
用後の焼却・埋設等の処理上の問題があることから、生
分解性樹脂発泡体への転換が図られるようになった。そ
の一つの方法として、生分解性のある澱粉を主成分とす
る樹脂発泡体の開発が進められたが、これらは、いずれ
も、耐湿性がなく、湿気を吸ってへたるので、湿度の高
いところでは使用することができなかった。そこで、耐
水性のある合成樹脂と澱粉とからなる複合樹脂発泡体が
開発されたが、廃棄後に澱粉の部分は微生物により分解
されても、合成樹脂の部分が長期に分解されずに残ると
いう問題があった。本発明は、このような生崩壊性樹脂
発泡体の改良に関するものである。TECHNICAL FIELD The present invention relates to a biodegradable resin foam having moisture resistance. BACKGROUND ART Conventionally, resin foams such as expanded polystyrene have been used as buffers for trays of fresh foods, containers for cup noodles, home electric appliances and the like. However, synthetic resin products such as polystyrene have been converted to biodegradable resin foams because of problems in processing such as incineration and burying after use. As one of the methods, development of resin foams containing biodegradable starch as a main component has been promoted, but none of these have moisture resistance, and because they absorb moisture, they are humid. By the way could not be used. Thus, a composite resin foam comprising a water-resistant synthetic resin and starch has been developed. However, even if the starch portion is decomposed by microorganisms after disposal, the synthetic resin portion remains without being decomposed for a long time. was there. The present invention relates to the improvement of such a biodegradable resin foam.
【０００２】[0002]
【従来の技術】従来、りんご等の果実や陶磁器を梱包し
輸送する際の緩衝材として、藁や籾殻等の天然材料をそ
のまま利用したり、木綿や古新聞紙等の天然材料を多少
加工したものを利用したりしてきた。その後、合成樹脂
産業の発展とともに、ポリスチレン発泡体が開発される
と、ポリスチレン発泡体は、機械部品や電機部品や家電
製品等の緩衝材だけでなく、生鮮食料品のトレーやカッ
プ麺の容器にまで利用されるようになった。しかしなが
ら、これらのポリスチレン発泡体を初め、他の食料品の
包装や日用品・家具等に使用される合成樹脂製品は、使
用後ゴミとして廃棄されると、焼却すれば、高温になり
焼却炉を損傷し、埋立地等に投棄すれば、藁や木綿等の
天然物とは異なり、微生物により分解されることなく、
何時までも嵩高のまま残って、その土地の植物の生育に
支障を来たすとともに、地盤の安定化を損ない、また、
時として、鳥や野性動物や魚等に誤食され、これらの動
物の健康をそこなう等の問題が発生した。そのため、生
分解性プラスチックの開発が進められた。2. Description of the Related Art Conventionally, natural materials such as straw and rice hulls have been used as they are as cushioning materials for packing and transporting fruits and ceramics such as apples, and some natural materials such as cotton and old newspaper have been processed. And have used it. Later, with the development of the synthetic resin industry, polystyrene foam was developed.Polystyrene foam was used not only in cushioning materials for mechanical parts, electrical parts and home appliances, but also in trays for fresh food and containers for cup noodles. Until it was used. However, synthetic resin products used in the packaging of other foodstuffs, daily necessities, furniture, etc., including these polystyrene foams, are disposed of as garbage after use. However, unlike natural products such as straw and cotton, if they are dumped in landfills, they will not be decomposed by microorganisms,
It will remain bulky for a long time, hindering the growth of the local plants, impairing the stability of the ground,
Occasionally, birds, wild animals, fish, and the like have inadvertently eaten the food, causing problems such as impairing the health of these animals. Therefore, development of biodegradable plastics has been promoted.
【０００３】このような状況下で、これまで生分解性プ
ラスチックについて多数の発明がなされてきた。その一
つには、とうもろこし等の澱粉にポリエチレンやポリプ
ロピレン等を混入したプラスチックがあり、例えば、特
開平７−２５８４５３号公報に開示された熱可塑性澱粉
と熱可塑性ポリマーとからなる生分解性プラスチック等
があげられる。このような澱粉含有プラスチックは、土
壌中に廃棄されると、混入された澱粉の部分だけが微生
物によって分解され、それによってプラスチックが多孔
質化されて表面積が増え、それによって合成樹脂成分も
風化作用等を受け易くなると考えられているものであ
り、狭義には、生崩壊性樹脂と呼ばれているものであ
る。Under such circumstances, many inventions have been made on biodegradable plastics. One of them is a plastic in which corn or the like is mixed with polyethylene or polypropylene, such as a biodegradable plastic comprising a thermoplastic starch and a thermoplastic polymer disclosed in JP-A-7-258453. Is raised. When such starch-containing plastics are discarded in soil, only the portion of the contaminated starch is decomposed by microorganisms, thereby making the plastic porous and increasing its surface area. It is considered that the resin is susceptible to the like, and in a narrow sense, is called a biodegradable resin.
【０００４】前述の澱粉含有プラスチックには、生分解
性の澱粉の部分には耐水性がなく、一方、耐水性の合成
樹脂部分は微生物によって分解されないという問題があ
ることから、種々の発明がなされている。例えば、ポリ
ビニールアルコールは、土壌中のシュードモナス・プチ
ダで分解されることが知られるようになって、澱粉に混
入するプラスチックとして、ポリビニールアルコール系
を使用することが試みられ、特開平６−１６８５７号公
報、特開平６−８７９６９号公報、特開平６−２２８３
５４号公報等には、合成樹脂成分としてエチレン−酢酸
ビニル共重合体を使用することが開示されており、更
に、特開平６−２７１６９３号公報、特開平６−２７１
６９４号公報、平６−２７１６９５号公報等には、合成
樹脂成分としてポリビニルアルコール系樹脂を使用する
ことが開示されている。The above-mentioned starch-containing plastics have various inventions because the biodegradable starch portion has no water resistance and the water-resistant synthetic resin portion is not decomposed by microorganisms. ing. For example, it has been known that polyvinyl alcohol is decomposed by Pseudomonas putida in soil, and attempts have been made to use polyvinyl alcohol as a plastic mixed with starch. JP, JP-A-6-87969, JP-A-6-2283
No. 54 and the like disclose the use of an ethylene-vinyl acetate copolymer as a synthetic resin component, and further disclosed in JP-A-6-271693 and JP-A-6-271.
Japanese Patent Application Laid-Open Nos. 694 and 6-271695 disclose the use of a polyvinyl alcohol resin as a synthetic resin component.
【０００５】しかしながら、前述の澱粉含有プラスチッ
クは、いずれも、耐水性や耐湿性に乏しく、梱包用の緩
衝用発泡体として使用する場合等には、ポリエチレンフ
ィルム等で作った防湿用の袋に入れて使用することが必
要であり、袋への挿入、袋の破れに対する注意や点検、
使用後の袋の廃棄等の面倒な作業があった。また、梱包
品が全く濡れるおそれがない場合でも、緩衝用発泡体
を、家電製品や機械部品の梱包にそのまま使用すれば、
空気中の湿度を吸収して発泡体がへたり、収納した物品
との間に隙間ができて、緩衝材としての機能が損なわ
れ、あるいは、果物や野菜の梱包に使用すれば、果物や
野菜の水分を吸収して発泡体が泥状化し、緩衝材として
の機能が全くなくなる等の問題が発生していた。このよ
うな問題を解決するため、本出願人は、特願平８−２６
５０３０号の明細書において、澱粉、ポリビニールアル
コール、及び、脂肪族ポリエステルからなる耐湿性生分
解樹脂発泡体、並びに、澱粉、ポリビニールアルコー
ル、及び、ポリプロピレンからなる耐湿性生分解樹脂発
泡体を開示した。[0005] However, the above-mentioned starch-containing plastics are all poor in water resistance and moisture resistance, and when used as a cushioning foam for packing, they are put in a moisture-proof bag made of a polyethylene film or the like. It is necessary to insert and insert into the bag, pay attention to and check for tearing of the bag,
There was troublesome work such as disposal of bags after use. In addition, even if there is no danger of the package being wet at all, if the foam for cushioning is used as it is for packaging home appliances and machine parts,
If the foam absorbs the humidity in the air, the foam will fall off, and a gap will be created between the stored articles, impairing the function as a cushioning material, or if used for packing fruits and vegetables, fruits and vegetables This causes the foam to become muddy due to the absorption of water, and the function as a cushioning material is completely lost. In order to solve such a problem, the present applicant has filed Japanese Patent Application No. Hei 8-26.
No. 5030 discloses a moisture-resistant biodegradable resin foam composed of starch, polyvinyl alcohol and aliphatic polyester, and a moisture-resistant biodegradable resin foam composed of starch, polyvinyl alcohol and polypropylene did.
【０００６】[0006]
【発明が解決しようとする課題】特願平８−２６５０３
０号の明細書において開示した澱粉、ポリビニールアル
コール、及び、脂肪族ポリエステルからなる耐湿性生分
解樹脂発泡体は、高い耐湿性を有し、生分解性を有する
素材からだけからなるが、高価であり、また、同明細書
に開示したポリビニールアルコール、及び、ポリプロピ
レンからなる耐湿性生分解樹脂発泡体は、高い耐湿性を
有するが、生分解性のないポリプロピレンを含んでお
り、生崩壊性を有していても完全な生分解性を有してい
ないという問題があった。発明が解決しようとする課題
は、高い耐湿性を有すると同時に、完全な生分解性を有
し、かつ、従来のプラスチック発泡体に対抗しうるほど
安価な生分解樹脂発泡体を提供することにある。Problems to be Solved by the Invention Japanese Patent Application No. 8-26503
The moisture-resistant biodegradable resin foam comprising starch, polyvinyl alcohol, and aliphatic polyester disclosed in the specification of No. 0 has high moisture resistance and consists only of a material having biodegradability, but is expensive. In addition, the polyvinyl alcohol disclosed in the specification and the moisture-resistant biodegradable resin foam made of polypropylene has high moisture resistance, but contains polypropylene that is not biodegradable. However, there is a problem that it does not have complete biodegradability even if it has The problem to be solved by the invention is to provide a biodegradable resin foam having high moisture resistance, complete biodegradability, and inexpensive enough to compete with conventional plastic foams. is there.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前述の問
題を解決するため、主として、澱粉６０〜８０重量部、
ポリプロピレン樹脂２０〜４０重量、長鎖脂肪酸又はそ
のエステル０．６〜６重量部、及び、鉄の長鎖脂肪酸塩
０．１〜０．５重量部からなることを特徴とする生分解
樹脂発泡体（以下「第１発明」という）、溶融したポリ
エチレン樹脂又はポリプロピレン樹脂１００重量部に、
乾燥した澱粉２０〜６０重量部、脂肪又は長鎖脂肪酸１
〜１５重量部、及び、鉄の長鎖脂肪酸塩１〜８重量部を
加え、更に必要に応じて、酸化促進剤や助触媒等を加え
てよく混練して生分解性樹脂組成物を製造し、得られた
生分解性樹脂組成物１０〜３０重量部にポリプロピレン
樹脂７０〜９０重量部を加えて溶融混練して骨格樹脂組
成物を製造し、得られた骨格樹脂組成物２０〜４０部
に、発泡剤１〜５重量部、水８〜１５重量部、澱粉６０
〜８０重量部を加えて、エクストルーダーで押し出して
発泡させることを特徴とする第１発明に係わる生分解樹
脂発泡体の製造方法（以下「第２発明」という）、及
び、溶融したポリエチレン樹脂又はポリプロピレン樹脂
１００重量部に、乾燥した澱粉２０〜６０重量部、脂肪
又は長鎖脂肪酸１〜１５重量部、及び、鉄の長鎖脂肪酸
塩１〜８重量部を加え、更に必要に応じて、酸化促進剤
や助触媒等を加えてよく混練して生分解性樹脂組成物を
製造し、得られた生分解性樹脂組成物ペレット２〜１２
重量部に、ポリプロピレン樹脂ペレット１４〜３６重量
部、発泡剤１〜５重量部、水８〜１５重量部を加え、更
に澱粉粉末６０〜８０重量部を加えて、二軸エクストル
ーダーに供給し、各ペレットが充分溶融する温度で混練
した後、高温高圧で押し出して発泡させることを特徴と
する第１発明に係わる生分解樹脂発泡体の製造方法（以
下「第３発明」という）を提供する。Means for Solving the Problems To solve the above-mentioned problems, the present inventors have mainly used starch at 60 to 80 parts by weight,
A biodegradable resin foam comprising 20 to 40 parts by weight of a polypropylene resin, 0.6 to 6 parts by weight of a long-chain fatty acid or an ester thereof, and 0.1 to 0.5 part by weight of a long-chain fatty acid salt of iron. (Hereinafter referred to as "first invention"), 100 parts by weight of the molten polyethylene resin or polypropylene resin,
20 to 60 parts by weight of dried starch, fat or long-chain fatty acid 1
To 15 parts by weight, and 1 to 8 parts by weight of a long-chain fatty acid salt of iron, and if necessary, further add an oxidation promoter, a co-catalyst, etc. and knead well to produce a biodegradable resin composition. And adding 70 to 90 parts by weight of a polypropylene resin to 10 to 30 parts by weight of the obtained biodegradable resin composition and melt-kneading to produce a skeletal resin composition, and obtaining 20 to 40 parts of the obtained skeletal resin composition. 1 to 5 parts by weight of a foaming agent, 8 to 15 parts by weight of water, starch 60
A method for producing a biodegradable resin foam according to the first invention (hereinafter referred to as a "second invention") characterized by adding to 80 parts by weight, extruding with an extruder, and foaming. 20 to 60 parts by weight of dried starch, 1 to 15 parts by weight of a fat or a long-chain fatty acid, and 1 to 8 parts by weight of a long-chain fatty acid salt of iron are added to 100 parts by weight of a polypropylene resin. A biodegradable resin composition is produced by adding an accelerator, a co-catalyst, etc. and kneading well to produce the biodegradable resin composition pellets 2 to 12.
Parts by weight, 14 to 36 parts by weight of polypropylene resin pellets, 1 to 5 parts by weight of a foaming agent, 8 to 15 parts by weight of water, 60 to 80 parts by weight of starch powder, and supply to a biaxial extruder, A method for producing a biodegradable resin foam according to the first invention (hereinafter, referred to as "third invention") is characterized in that the pellets are kneaded at a temperature at which they are sufficiently melted, extruded at a high temperature and a high pressure, and foamed.
【０００８】第１発明に係わる生分解樹脂発泡体は、主
として、澱粉６０〜８０重量部、ポリプロピレン樹脂２
０〜４０重量、長鎖脂肪酸又はそのエステル０．６〜６
重量部、及び、鉄の長鎖脂肪酸塩０．１〜０．５重量部
からなることを特徴としている。この澱粉には、後述す
る生分解性樹脂組成物に含まれる澱粉と、それにポリプ
ロピレン樹脂を添加して製造された骨格樹脂組成物に添
加される澱粉が含まれる。ポリプロピレン樹脂には、生
分解性樹脂組成物に加えられるポリプロピレン樹脂が含
まれ、更に、生分解性樹脂組成物にポリプロピレン樹脂
が含まれている場合には、それも含まれる。長鎖脂肪酸
には、パルミチン酸、ステアリン酸、オレイン酸等の天
然の油脂に含まれるものであり、そのエステルには、天
然の油脂が含まれており、いずれも生分解性を有するも
のであって、酸化されて過酸化物を形成し、ポリプロピ
レン樹脂やポリエチレン樹脂の炭素鎖の酸化切断に寄与
するものである。鉄の長鎖脂肪酸塩は、前述の天然の油
脂に含まれる脂肪酸の鉄塩又は水酸化鉄塩であり、長鎖
脂肪酸やそのエステルの酸化触媒となるものである。ま
た、これ以外に含まれるものとしては、生分解性樹脂組
成物にポリエチレン樹脂を使用した場合は、そのポリエ
チレンが含まれ、炭酸カルシム等の発泡剤を使用した場
合は、その残存化合物が含まれ、更に、ベンゾフェノン
のような芳香族ケトン等の酸化促進剤、フェノール類等
の酸化防止剤、界面活性剤、顔料、充填剤等が含まれ
る。[0008] The biodegradable resin foam according to the first invention mainly comprises 60 to 80 parts by weight of starch and 2 parts by weight of polypropylene resin 2.
0-40 weight, long chain fatty acid or its ester 0.6-6
And 0.1 to 0.5 parts by weight of a long-chain fatty acid salt of iron. This starch includes starch contained in a biodegradable resin composition described later and starch added to a skeleton resin composition produced by adding a polypropylene resin thereto. The polypropylene resin includes a polypropylene resin added to the biodegradable resin composition, and further includes a polypropylene resin when the biodegradable resin composition includes the polypropylene resin. Long-chain fatty acids are those contained in natural fats and oils such as palmitic acid, stearic acid and oleic acid, and their esters contain natural fats and oils, all of which are biodegradable. Then, it is oxidized to form a peroxide, which contributes to oxidative cleavage of a carbon chain of a polypropylene resin or a polyethylene resin. The iron long-chain fatty acid salt is an iron salt or iron hydroxide of a fatty acid contained in the above-described natural fats and oils, and serves as an oxidation catalyst for long-chain fatty acids and esters thereof. In addition, as other components included, when a polyethylene resin is used in the biodegradable resin composition, the polyethylene is included, and when a blowing agent such as calcium carbonate is used, the residual compound is included. Further, an oxidation promoter such as an aromatic ketone such as benzophenone, an antioxidant such as a phenol, a surfactant, a pigment, a filler and the like are included.
【０００９】澱粉とポリプロピレン樹脂の比率ついて
は、一般に、澱粉の量が多ければ空隙率の高い柔らかい
ものが得られ、ポリプロピレン樹脂の量が多ければ空隙
率の低い固いものが得られる。通常の発泡体について
は、澱粉とポリプロピレン樹脂の比率は、６０：４０〜
８０：２０の範囲である。長鎖脂肪酸又はそのエステル
の量は、ポリプロピレン樹脂の量が多くなるにつれて、
また、ポリプロピレン樹脂の分解速度を速くするにつれ
て多くなる。また、鉄の長鎖脂肪酸塩の量は、長鎖脂肪
酸又はそのエステルの量が多くなるにつれて、また、ポ
リプロピレン樹脂の分解速度を速くするにつれて多くな
る。Regarding the ratio of starch to polypropylene resin, generally, a large amount of starch results in a soft material having a high porosity, and a large amount of polypropylene resin results in a hard material having a low porosity. For ordinary foams, the ratio of starch to polypropylene resin is between 60:40 and
The range is 80:20. The amount of long-chain fatty acids or esters thereof, as the amount of polypropylene resin increases,
Further, it increases as the decomposition rate of the polypropylene resin increases. The amount of the long-chain fatty acid salt of iron increases as the amount of the long-chain fatty acid or its ester increases, and as the decomposition rate of the polypropylene resin increases.
【００１０】第２発明に係わる生分解樹脂発泡体の製造
方法は、第１工程として、溶融したポリエチレン樹脂又
はポリプロピレン樹脂１００重量部に、乾燥した澱粉２
０〜６０重量部、脂肪又は長鎖脂肪酸１〜１５重量部、
鉄の長鎖脂肪酸塩１〜８重量部、更に必要に応じて、酸
化促進剤や助触媒等を加えてよく混練して生分解性樹脂
組成物を製造する工程、第２工程として、この生分解性
樹脂組成物１０〜３０重量部にポリプロピレン樹脂７０
〜９０重量部を加えて溶融混練して骨格樹脂組成物を製
造する工程、第３工程として、この骨格樹脂組成物２０
〜４０部に発泡剤１〜５重量部、水８〜１５重量部、澱
粉６０〜８０重量部を加えてエクストルーダーで押し出
して発泡体を製造する工程からなっている。In the method for producing a biodegradable resin foam according to the second invention, as a first step, 100 parts by weight of a molten polyethylene resin or polypropylene resin is added to a dried starch 2
0 to 60 parts by weight, 1 to 15 parts by weight of fat or long-chain fatty acid,
1 to 8 parts by weight of a long-chain fatty acid salt of iron, and if necessary, an oxidation promoter, a co-catalyst, and the like are added and kneaded well to produce a biodegradable resin composition. 10 to 30 parts by weight of the decomposable resin composition contains polypropylene resin 70
To 90 parts by weight and melt-kneading to produce a skeleton resin composition. As a third step, the skeleton resin composition 20
1 to 5 parts by weight of a foaming agent, 8 to 15 parts by weight of water, and 60 to 80 parts by weight of starch to 40 to 40 parts, and extrude with an extruder to produce a foam.
【００１１】第３発明に係わる生分解樹脂発泡体の製造
方法は、第１工程として、第２発明と同様な生分解性樹
脂組成物を製造する工程、第２工程として、生分解性樹
脂組成物ペレット２〜１２重量部に、ポリプロピレン樹
脂ペレット１４〜３６重量部、発泡剤１〜５重量部、水
８〜１５重量部を加え、更に澱粉粉末６０〜８０重量部
を加えて、二軸エクストルーダーに供給し、各ペレット
が充分溶融する温度で混練した後、高温高圧で押し出し
て発泡体を製造する工程からなっている。すなわち、第
３発明は、第２発明の第２工程と第３工程とを一緒し
て、工程を合理化したものである。なお、第２発明及び
第３発明で使用される発泡剤には、通常炭酸カルシウム
が使用されるが、必ずしもこれに限定されるものではな
い。The method for producing a biodegradable resin foam according to the third invention comprises, as a first step, a step of producing a biodegradable resin composition similar to that of the second invention, and as a second step, a biodegradable resin composition 2 to 12 parts by weight of product pellets, 14 to 36 parts by weight of polypropylene resin pellets, 1 to 5 parts by weight of a foaming agent, 8 to 15 parts by weight of water, and 60 to 80 parts by weight of starch powder are added. After supplying the mixture to a ruder and kneading at a temperature at which each pellet is sufficiently melted, the mixture is extruded at a high temperature and a high pressure to produce a foam. That is, in the third invention, the steps are rationalized by combining the second step and the third step of the second invention. Note that calcium carbonate is usually used as the blowing agent used in the second invention and the third invention, but is not necessarily limited thereto.
【００１２】なお、第２発明及び第３発明において、澱
粉を添加する場合は、骨格樹脂組成物、又は、生分解性
樹脂組成物ペレットとポリプロピレン樹脂ペレットとの
混合物に、予め水と発泡剤とを混合してよく攪拌して水
を均一に分散させてから、澱粉を混合する方が、澱粉の
局所的な水分むらがなくなり、水分が均一化されるので
好ましい。In the second and third inventions, when starch is added, water and a foaming agent are added to a skeleton resin composition or a mixture of biodegradable resin composition pellets and polypropylene resin pellets in advance. It is preferable to mix and mix well and to disperse the water uniformly, and then to mix the starch, since the local moisture unevenness of the starch is eliminated and the moisture is homogenized.
【００１３】[0013]
【作用】従来の澱粉含有プラスチックには、合成樹脂部
分は微生物によって分解されないで長期間残るという問
題があった。その原因の一つは、疎水性のポリエチレン
樹脂又はポリプロピレン樹脂に親水性の澱粉を混合する
と巨視的には均一になっていても微視的には必ずしも均
一に混合されておらず、澱粉が生分解された後の形状も
目の粗い多孔質であることにあった。しかし、本発明に
おける生分解性樹脂組成物は、乾燥した澱粉を使用して
いるので、疎水性の樹脂とも均一に混合され、澱粉が生
分解された後には緻密な多孔質のものが得られ、表面積
が非常に大きくなっている。また、ここで使用される天
然脂肪や長鎖脂肪酸は、生分解性があるだけでなく、長
鎖の部分がポリオレフィンと親和性を有し、カルボン酸
の部分が澱粉との親和性を有している。更に、ここで使
用する酸化触媒にも、鉄の長鎖脂肪酸塩を使用している
ので、天然脂肪や長鎖脂肪酸と親和性を有し、ポリオレ
フィンや澱粉とも親和性を有するものである。従って、
本発明における生分解性樹脂組成物では、澱粉が生分解
した後は、メチレ鎖が急速に酸化切断されて、かなりの
速度でポリオレフィンが生分解されるものと推定され
る。なお、１４Ｃを標識として合成したポリエチレン樹
脂を用いて製造した生分解性樹脂組成物を土壌におい
て、発生する二酸化炭素を調べたところ、１４ＣＯ２が
検出されているので、ポリエチレン樹脂が生分解されて
いるのは確実と考えられる。The conventional starch-containing plastic has a problem that the synthetic resin portion remains for a long time without being decomposed by microorganisms. One of the causes is that when hydrophilic starch is mixed with hydrophobic polyethylene resin or polypropylene resin, even if macroscopically uniform, microscopically, they are not always uniformly mixed, and starch is not produced. The shape after decomposition was also found to be coarse and porous. However, since the biodegradable resin composition of the present invention uses dried starch, it is also uniformly mixed with a hydrophobic resin, and after the starch is biodegraded, a dense porous product is obtained. , The surface area is very large. The natural fats and long-chain fatty acids used here are not only biodegradable, but also have a long-chain part having an affinity for polyolefin and a carboxylic acid part having an affinity for starch. ing. Furthermore, since the long-chain fatty acid salt of iron is used also in the oxidation catalyst used here, it has affinity with natural fats and long-chain fatty acids, and also has affinity with polyolefins and starch. Therefore,
In the biodegradable resin composition of the present invention, it is presumed that after the starch is biodegraded, the methylene chain is rapidly oxidatively cleaved, and the polyolefin is biodegraded at a considerable rate. In addition, when the biodegradable resin composition manufactured using the polyethylene resin synthesized using 14 C as a label was examined for carbon dioxide generated in the soil, 14 CO 2 was detected. It is believed that it has been done.
【００１４】前述の生分解性樹脂組成物は、澱粉が乾燥
されており、極めて微細に樹脂中に分散しているので、
発泡されるのは極めて困難であった。本発明に係わる発
泡体では、発泡体の強度を増すために使用するポリプロ
ピレン樹脂の生分解性を高めために、生分解性樹脂組成
物を混入し、また、発泡させるためには生分解性樹脂組
成物とは別に澱粉を使用している。従って、発泡させる
澱粉を添加した後は、あまり攪拌又は混練し過ぎると、
澱粉粒子が破壊されるので発泡し難くなり、また、細か
く分散され気泡が緻密になり過ぎるのでこの好ましくな
い。なお、あまり攪拌することなく澱粉に均一に水分を
吸着するためには、骨格樹脂組成物、又は、生分解性樹
脂組成物ペレットとポリプロピレン樹脂ペレットとの混
合物に、予め水と発泡剤とを混合してよく攪拌して水を
均一に分散させてから、澱粉を混合するのが好ましい。In the above-mentioned biodegradable resin composition, starch is dried and very finely dispersed in the resin.
It was extremely difficult to foam. In the foam according to the present invention, a biodegradable resin composition is mixed to increase the biodegradability of the polypropylene resin used to increase the strength of the foam, Starch is used separately from the composition. Therefore, after adding the starch to be foamed, if too much stirring or kneading,
This is undesirable because the starch particles are destroyed and foaming becomes difficult, and finely dispersed and air bubbles become too dense. In order to uniformly adsorb moisture to starch without excessive stirring, water and a foaming agent are previously mixed with a skeleton resin composition or a mixture of biodegradable resin composition pellets and polypropylene resin pellets. It is preferable to mix the starch after stirring to disperse the water uniformly.
【００１５】[0015]
１．生分解樹脂発泡体の製造 〔実施例１〕溶融したポリプロピレン樹脂１００重量部
に、乾燥した澱粉５０重量部、脂肪又は長鎖脂肪酸１２
重量部、及び、鉄の水酸化ステアリン酸塩６重量部を加
え、微小量の銅のステアリン酸塩、ベンゾフェノンを加
えてよく混練して生分解性樹脂組成物を製造しペレット
とした。ポリプロピレン樹脂ペレット２４重量部に前記
生分解性樹脂組成物ペレット６重量部を加え１４０℃で
混練し骨格樹脂組成物のペレットを製造した。この骨格
樹脂組成物ペレット３０部に、コーンスターチ粉末６７
重量部と炭酸カルシウム３重量部を加え、更に水１０重
量部を加えて、中間に練り戻し装置を付けた２軸エクス
トルダーに供給し、逐次温度を上げながら混練し、１８
０℃の金型の内径２．４ｍｍのノズルから大気中に押し
出し生分解樹脂発泡体（以下「発泡体１〕という）をえ
た。1. Example 1 Production of biodegradable resin foam Example 1 100 parts by weight of molten polypropylene resin, 50 parts by weight of dried starch, 12 parts of fat or long-chain fatty acid
Parts by weight and 6 parts by weight of iron hydroxide stearate were added, and minute amounts of copper stearate and benzophenone were added and kneaded well to produce a biodegradable resin composition and pelletized. 6 parts by weight of the biodegradable resin composition pellets were added to 24 parts by weight of polypropylene resin pellets, and kneaded at 140 ° C. to produce pellets of the skeleton resin composition. 30 parts of the skeleton resin composition pellets are mixed with corn starch powder 67
Parts by weight, 3 parts by weight of calcium carbonate, and 10 parts by weight of water, and the mixture is fed to a twin-screw extruder equipped with an intermediate kneading device.
A biodegradable resin foam (hereinafter referred to as "foam 1") was extruded into the atmosphere from a 2.4 mm inner diameter nozzle of a mold at 0 ° C.
【００１６】〔実施例２〕ポリプロピレン樹脂ペレット
２４重量部に、実施例１の生分解性樹脂組成物ペレット
６重量部、炭酸カルシウム３重量部、水１０重量部を加
えて、ミキサーで３０分間充分混合した後、コーンスタ
ーチ粉末６７重量部を加えて更に３０分間攪拌した後、
２軸エクストルダーに供給し、逐次温度を上げながら混
練し、１８０℃の金型の内径２．４ｍｍのノズルから大
気中に押し出し生分解樹脂発泡体（以下「発泡体２〕と
いう）をえた。Example 2 To 24 parts by weight of polypropylene resin pellets, 6 parts by weight of the biodegradable resin composition pellets of Example 1, 3 parts by weight of calcium carbonate and 10 parts by weight of water were added, and the mixture was sufficiently mixed for 30 minutes. After mixing, 67 parts by weight of corn starch powder was added, and the mixture was further stirred for 30 minutes.
The mixture was supplied to a twin-screw extruder, kneaded while sequentially increasing the temperature, and extruded into the atmosphere from a nozzle having an inner diameter of 2.4 mm of a mold at 180 ° C. to obtain a biodegradable resin foam (hereinafter referred to as “foam 2”).
【００１７】〔実施例３〕コーンスターチ粉末６７重量
部、ポリプロピレン樹脂ペレット２４重量部、実施例１
の生分解性樹脂組成物ペレット６重量部、及び、炭酸カ
ルシウム３重量部からなる混合物を、エクストルーダー
に供給し、水１０重量部を加えてながら、逐次温度を上
げながら混練し、１８０℃の金型の内径２．４ｍｍのノ
ズルから大気中に押し出し生分解樹脂発泡体（以下「発
泡体３〕という）をえた。Example 3 67 parts by weight of corn starch powder, 24 parts by weight of polypropylene resin pellets, Example 1
A mixture consisting of 6 parts by weight of the biodegradable resin composition pellets and 3 parts by weight of calcium carbonate was supplied to an extruder, and kneaded while gradually increasing the temperature while adding 10 parts by weight of water. A biodegradable resin foam (hereinafter referred to as "foam 3") was extruded into the atmosphere from a nozzle having an inner diameter of 2.4 mm of the mold.
【００１８】２．生分解樹脂発泡体の特性 実施例１〜３で得られた発泡体１〜発泡体３の特性は表
１のとおりであり、緩衝材として優れたものが得られる
ことがわかった。2. Properties of Biodegradable Resin Foam The properties of foams 1 to 3 obtained in Examples 1 to 3 are as shown in Table 1, and it was found that an excellent cushioning material was obtained.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】本発明に係わる生分解樹脂発泡体および
その製造方法は、前述のような構成と作用をするので、
充分な生分解性と耐湿性を備え、優れたクッション性、
感触、耐衝撃性を有するものを提供することができ、廃
棄等の際に問題のあるポリスチレン等に代わって使用す
ることができ、国民の生活環境の保全に寄与するところ
大きいものである。The biodegradable resin foam and the method for producing the same according to the present invention operate as described above,
With sufficient biodegradability and moisture resistance, excellent cushioning,
It can provide a material having a touch and impact resistance, and can be used in place of polystyrene or the like, which has a problem in disposal, etc., and greatly contributes to the preservation of the living environment of the people.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年３月１０日[Submission date] March 10, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１５】[0015]
【発明の実施の形態】 １．生分解樹脂発泡体の製造 〔実施例１〕溶融したポリプロピレン樹脂１００重量部
に、乾燥した澱粉５０重量部、長鎖脂肪酸１２重量部、
及び、鉄の水酸化ステアリン酸塩６重量部を加え、微小
量の銅のステアリン酸塩、ベンゾフェノンを加えてよく
混練して生分解性樹脂組成物を製造しペレットとした。
ポリプロピレン樹脂ペレット２４重量部に前記生分解性
樹脂組成物ペレット６重量部を加え１４０℃で混練し骨
格樹脂組成物のペレットを製造した。この骨格樹脂組成
物ペレット３０部に、コーンスターチ粉末６７重量部と
炭酸カルシウム３重量部を加え、更に水１０重量部を加
えて、中間に練り戻し装置を付けた２軸エクストルダー
に供給し、逐次温度を上げながら混練し、１８０℃の金
型の内径２．４ｍｍのノズルから大気中に押し出し生分
解樹脂発泡体（以下「発泡体１〕という）をえた。BEST MODE FOR CARRYING OUT THE INVENTION Production of Biodegradable Resin Foam [Example 1] 100 parts by weight of molten polypropylene resin, 50 parts by weight of dried starch , 12 parts by weight of long- chain fatty acid,
Then, 6 parts by weight of iron hydroxide stearate was added, and minute amounts of copper stearate and benzophenone were added and kneaded well to produce a biodegradable resin composition and pelletized.
6 parts by weight of the biodegradable resin composition pellets were added to 24 parts by weight of polypropylene resin pellets, and kneaded at 140 ° C. to produce pellets of the skeleton resin composition. To 30 parts of the skeleton resin composition pellets, 67 parts by weight of corn starch powder and 3 parts by weight of calcium carbonate are added, and 10 parts by weight of water are further added, and the mixture is supplied to a twin-screw extruder equipped with an intermediate kneading device. The mixture was kneaded while increasing the temperature, and extruded into the atmosphere from a nozzle having a 180 mm inner diameter of 2.4 mm to obtain a biodegradable resin foam (hereinafter referred to as "foam 1").
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 23/12 Ｃ０８Ｌ 23/12 //(Ｃ０８Ｋ 5/04 5:09 5:10） ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 23/12 C08L 23/12 // (C08K 5/04 5:09 5:10)
Claims (3)
プロピレン樹脂２０〜４０重量、長鎖脂肪酸又はそのエ
ステル０．６〜６重量部、及び、鉄の長鎖脂肪酸塩０．
１〜０．５重量部からなることを特徴とする生分解樹脂
発泡体1. Mainly 60 to 80 parts by weight of starch, 20 to 40 parts by weight of a polypropylene resin, 0.6 to 6 parts by weight of a long-chain fatty acid or its ester, and 0.1 to 6 parts by weight of a long-chain fatty acid salt of iron.
A biodegradable resin foam comprising 1 to 0.5 parts by weight
ピレン樹脂１００重量部に、乾燥した澱粉２０〜６０重
量部、脂肪又は長鎖脂肪酸１〜１５重量部、及び、鉄の
長鎖脂肪酸塩１〜８重量部を加え、更に必要に応じて、
酸化促進剤や助触媒等を加えてよく混練して生分解性樹
脂組成物を製造し、得られた生分解性樹脂組成物１０〜
３０重量部にポリプロピレン樹脂７０〜９０重量部を加
えて溶融混練して骨格樹脂組成物を製造し、得られた骨
格樹脂組成物２０〜４０部に発泡剤１〜５重量部、水８
〜１５重量部、澱粉６０〜８０重量部を加えて、エクス
トルーダーで押し出して発泡させることを特徴とする請
求項１記載の生分解樹脂発泡体の製造方法2. 100 parts by weight of molten polyethylene resin or polypropylene resin, 20 to 60 parts by weight of dried starch, 1 to 15 parts by weight of fat or long-chain fatty acid, and 1 to 8 parts by weight of iron long-chain fatty acid salt And, if necessary,
A biodegradable resin composition is prepared by adding an oxidation promoter, a cocatalyst, etc. and kneading well to produce a biodegradable resin composition.
70 to 90 parts by weight of a polypropylene resin is added to 30 parts by weight, and the mixture is melt-kneaded to produce a skeleton resin composition. 20 to 40 parts of the obtained skeleton resin composition are mixed with 1 to 5 parts by weight of a foaming agent and 8 parts of water.
2. The method for producing a biodegradable resin foam according to claim 1, wherein the foam is extruded by adding an extruder to the mixture, and adding to the mixture by extruding the extruder.
ピレン樹脂１００重量部に、乾燥した澱粉２０〜６０重
量部、脂肪又は長鎖脂肪酸１〜１５重量部、及び、鉄の
長鎖脂肪酸塩１〜８重量部を加え、更に必要に応じて、
酸化促進剤や助触媒等を加えてよく混練して生分解性樹
脂組成物を製造し、得られた生分解性樹脂組成物ペレッ
ト２〜１２重量部にポリプロピレン樹脂ペレット１４〜
３６重量部、発泡剤１〜５重量部、水８〜１５重量部を
加え、更に澱粉粉末６０〜８０重量部を加えて、二軸エ
クストルーダーに供給し、各ペレットが充分溶融する温
度で混練した後、高温高圧で押し出して発泡させること
を特徴とする請求項１記載の生分解樹脂発泡体の製造方
法3. 100 parts by weight of molten polyethylene resin or polypropylene resin, 20 to 60 parts by weight of dried starch, 1 to 15 parts by weight of fat or long-chain fatty acid, and 1 to 8 parts by weight of iron long-chain fatty acid salt And, if necessary,
A biodegradable resin composition is produced by adding an oxidation promoter, a co-catalyst, etc. and kneading well to produce a biodegradable resin composition pellet, and polypropylene resin pellet 14 to 12 to 12 parts by weight of the obtained biodegradable resin composition pellet.
36 parts by weight, 1 to 5 parts by weight of a foaming agent, 8 to 15 parts by weight of water, and 60 to 80 parts by weight of starch powder are added, and the mixture is supplied to a twin-screw extruder and kneaded at a temperature at which each pellet is sufficiently melted. 2. The method for producing a biodegradable resin foam according to claim 1, wherein the foam is extruded at a high temperature and a high pressure after foaming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9207049A JPH1112379A (en) | 1997-06-25 | 1997-06-25 | Biodegradable resin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9207049A JPH1112379A (en) | 1997-06-25 | 1997-06-25 | Biodegradable resin foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1112379A true JPH1112379A (en) | 1999-01-19 |
Family
ID=16533369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9207049A Pending JPH1112379A (en) | 1997-06-25 | 1997-06-25 | Biodegradable resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1112379A (en) |
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| CN1074435C (en) * | 1999-06-22 | 2001-11-07 | 沈阳南阳经贸集团有限公司 | Polynary degradable resin composition and its preparation process |
| CN1074433C (en) * | 1997-08-18 | 2001-11-07 | 清华紫光(集团)总公司 | Polyester type starch plastic |
| CN1081203C (en) * | 1999-02-11 | 2002-03-20 | 天津丹海股份有限公司 | Preparation of mother material for biodegradable plastics |
| JP2003012844A (en) * | 2001-07-02 | 2003-01-15 | Inoac Corp | Polyolefin foamed material and production method thereof |
| CN1114653C (en) * | 2000-01-12 | 2003-07-16 | 李小鲁 | Biologically degradable resin composition and its preparation and application |
| KR100657413B1 (en) | 2005-02-25 | 2006-12-13 | (주) 에코마인드 | Method for preparing photodegradable calcium carbonate composition and disposable container using it |
| CN103160012A (en) * | 2013-04-01 | 2013-06-19 | 天津超平新材料科技有限公司 | Oxygen-separating and degradable thin plastic film |
| CN104448398A (en) * | 2014-11-18 | 2015-03-25 | 东莞市方中运动制品有限公司 | Cassava degradable plastic as well as production process and production equipment thereof |
| IT202000016798A1 (en) * | 2020-07-10 | 2022-01-10 | Fondazione St Italiano Tecnologia | PROCESS FOR THE IMPROVEMENT OF THE BIODEGRADABILITY OF POLYOLEFIN MATERIALS |
-
1997
- 1997-06-25 JP JP9207049A patent/JPH1112379A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074433C (en) * | 1997-08-18 | 2001-11-07 | 清华紫光(集团)总公司 | Polyester type starch plastic |
| CN1081203C (en) * | 1999-02-11 | 2002-03-20 | 天津丹海股份有限公司 | Preparation of mother material for biodegradable plastics |
| CN1074435C (en) * | 1999-06-22 | 2001-11-07 | 沈阳南阳经贸集团有限公司 | Polynary degradable resin composition and its preparation process |
| CN1114653C (en) * | 2000-01-12 | 2003-07-16 | 李小鲁 | Biologically degradable resin composition and its preparation and application |
| JP2003012844A (en) * | 2001-07-02 | 2003-01-15 | Inoac Corp | Polyolefin foamed material and production method thereof |
| KR100657413B1 (en) | 2005-02-25 | 2006-12-13 | (주) 에코마인드 | Method for preparing photodegradable calcium carbonate composition and disposable container using it |
| CN103160012A (en) * | 2013-04-01 | 2013-06-19 | 天津超平新材料科技有限公司 | Oxygen-separating and degradable thin plastic film |
| CN104448398A (en) * | 2014-11-18 | 2015-03-25 | 东莞市方中运动制品有限公司 | Cassava degradable plastic as well as production process and production equipment thereof |
| IT202000016798A1 (en) * | 2020-07-10 | 2022-01-10 | Fondazione St Italiano Tecnologia | PROCESS FOR THE IMPROVEMENT OF THE BIODEGRADABILITY OF POLYOLEFIN MATERIALS |
| WO2022008570A1 (en) * | 2020-07-10 | 2022-01-13 | Fondazione Istituto Italiano Di Tecnologia | Process for the enhancement of the biodegradability of polyolefinic materials |
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