JP2001288228A - Biodegradable polymer modifier and its composition - Google Patents

Biodegradable polymer modifier and its composition

Info

Publication number
JP2001288228A
JP2001288228A JP2000101515A JP2000101515A JP2001288228A JP 2001288228 A JP2001288228 A JP 2001288228A JP 2000101515 A JP2000101515 A JP 2000101515A JP 2000101515 A JP2000101515 A JP 2000101515A JP 2001288228 A JP2001288228 A JP 2001288228A
Authority
JP
Japan
Prior art keywords
biodegradable polymer
monomer
weight
polymer
modifier
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
Application number
JP2000101515A
Other languages
Japanese (ja)
Inventor
Takashi Kurata
貴志 蔵田
Kenju Furuyama
建樹 古山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Techno UMG Co Ltd
Original Assignee
Techno Polymer Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Techno Polymer Co Ltd filed Critical Techno Polymer Co Ltd
Priority to JP2000101515A priority Critical patent/JP2001288228A/en
Publication of JP2001288228A publication Critical patent/JP2001288228A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming

Landscapes

  • Greenhouses (AREA)
  • Cultivation Receptacles Or Flower-Pots, Or Pots For Seedlings (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Protection Of Plants (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a modifier which is easily decomposed by microorganisms, is excellent in terms of global environment and biological environment, and is used for producing a natural rubber-base polymer with enhanced strengths and provide a composition of the same. SOLUTION: This modifier is prepared by the graft polymerization of (B) 5-99 wt.% monomer such as a carboxylated monomer (e.g. methacrylic acid), a hydroxylated monomer (e.g. 2-hydroxyethyl acrylate), or a glycidylated monomer (e.g. glycidyl acrylate) and (C) 0-94 wt.% other monomer (e.g. styrene) in the presence of (A) 1-95 wt.% rubbery polymer comprising natural rubber and/or an epoxidized natural rubber, the graft efficiency being 30 % or higher. A biodegradable polymer composition is provided which contains the modifier (in an amount of about 0.1-70 wt.%) and a natural-derived polymer (e.g. chitosan), a microorganism-synthesized polymer (e.g. polyhydroxybutyrate), or a chemically synthesized biodegradable polymer (e.g. polylactic acid).

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、生分解性ポリマー
改質剤及びその組成物に関し、更に詳しくは、生分解性
即ち微生物により分解されやすく、地球環境及び生物環
境的に優れ、しかも強度、伸び等の性能を改善する改質
剤及びその組成物に関するものである。本組成物は、農
業用フィルム、苗等の容器、スーパーの買い物袋用フィ
ルム等に広く利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable polymer modifier and a composition thereof, and more particularly, to a biodegradable polymer, that is, easily degraded by microorganisms, excellent in global environment and bioenvironment, and has strength, The present invention relates to a modifier for improving performance such as elongation and a composition thereof. The present composition is widely used for agricultural films, containers for seedlings, films for shopping bags in supermarkets, and the like.

【０００２】[0002]

【従来の技術】従来より、天然ゴムは天然物であるた
め、生分解性物質であることは知られている。しかし、
天然ゴムを使用した天然ゴム製品は、ゴム弾性などの物
理的性質を向上させるために、天然ゴムに硫黄等の加硫
剤や加硫促進剤、老化防止剤等のゴム薬剤を配合してい
るため、生分解性が低下し、一般には難分解性物質とみ
なされている。生分解性ポリマーが上市されているが、
強度、伸び等の性能が十分ではなく、工業的使用の展開
の大きな支障となっている。例えば、生分解性ポリマー
の強度や伸びを改善しようという試みとしては、微生物
合成系のポリヒドロキシブチレート（ＰＨＢ）と３−ヒ
ドロキシバリレート（３ＨＶ）との共重合による方法が
あるが、この方法はコストの点で好ましくない。一般的
に、強度や伸びを改善する方法として、ゴムを配合する
方法が試みられているが、ゴムと生分解性ポリマーとの
相溶性が十分でなく、強度や伸び等の性能が十分に改善
できなかった。2. Description of the Related Art Conventionally, it is known that natural rubber is a biodegradable substance because it is a natural product. But,
Natural rubber products using natural rubber are compounded with natural rubber with rubber agents such as vulcanizing agents such as sulfur, vulcanization accelerators, and anti-aging agents to improve physical properties such as rubber elasticity. Therefore, the biodegradability decreases, and it is generally regarded as a hardly decomposable substance. Biodegradable polymers are on the market,
The performance such as strength and elongation is not sufficient, which is a major obstacle to the development of industrial use. For example, as an attempt to improve the strength and elongation of a biodegradable polymer, there is a method based on copolymerization of microbial synthetic polyhydroxybutyrate (PHB) and 3-hydroxyvalerate (3HV). Is not preferred in terms of cost. In general, as a method of improving the strength and elongation, a method of compounding rubber has been tried, but the compatibility between the rubber and the biodegradable polymer is not sufficient, and the performance such as strength and elongation is sufficiently improved. could not.

【０００３】[0003]

【発明が解決しようとする課題】本発明は、上記実情に
鑑みてなされたものであり、豊富に存在する天然ゴムを
生分解性ポリマーと相溶するように変性させることによ
って、優れた強度と伸びを付与させ、更に生分解性にも
優れ環境への廃棄問題も解決した、低コストの生分解性
ポリマー改質剤及び生分解性ポリマー組成物を提供する
ものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has been developed by modifying abundant natural rubber so as to be compatible with a biodegradable polymer, thereby obtaining excellent strength and strength. It is an object of the present invention to provide a low-cost biodegradable polymer modifier and a biodegradable polymer composition which provide elongation, have excellent biodegradability, and solve the problem of disposal to the environment.

【０００４】[0004]

【課題を解決するための手段】本発明者らは、天然ゴム
を生分解性ポリマーと相溶するように変性させることに
よって優れた強度と伸びを実現する生分解性ポリマー組
成物を得るべく鋭意検討を重ねた結果、天然ゴム及び／
又はエポキシ化天然ゴムからなるゴム状重合体の存在下
に、単量体化合物をグラフト重合させ、天然物系生分解
性ポリマー、微生物合成系生分解性ポリマー及び化学合
成系生分解性ポリマーの群から選ばれる少なくとも一種
の生分解性ポリマーと所定の範囲内で配合することによ
り本目的を達成できることを見い出して、本発明を完成
した。即ち、本第１発明の生分解性ポリマー改質剤は、
天然ゴム及び／又はエポキシ化天然ゴムからなるゴム状
重合体（Ａ）１〜９５重量％の存在下に、カルボキシル
基含有単量体、ヒドロキシル基含有単量体、グリシジル
基含有単量体、アミド系単量体及びアミノ基含有単量体
の群から選ばれる少なくとも一種の単量体化合物（Ｂ）
５〜９９重量％、並びに他の単量体化合物（Ｃ）０〜９
４重量％（但し、上記（Ａ）、上記（Ｂ）及び上記
（Ｃ）の合計が１００重量％である。）をグラフト重合
して得られ、且つグラフト効率が３０％以上であること
を特徴とする。Means for Solving the Problems The present inventors have been keen to obtain a biodegradable polymer composition which achieves excellent strength and elongation by modifying natural rubber so as to be compatible with the biodegradable polymer. As a result of repeated studies, natural rubber and / or
Or a group of natural biodegradable polymers, microbial biodegradable polymers and chemically synthesized biodegradable polymers by graft polymerization of a monomer compound in the presence of a rubbery polymer composed of epoxidized natural rubber. The present invention has been completed by finding that the present object can be achieved by blending in a predetermined range with at least one biodegradable polymer selected from the group consisting of: That is, the biodegradable polymer modifier of the first invention is:
In the presence of 1 to 95% by weight of a rubbery polymer (A) comprising a natural rubber and / or an epoxidized natural rubber, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, a glycidyl group-containing monomer, an amide At least one monomer compound (B) selected from the group consisting of a series monomer and an amino group-containing monomer
5 to 99% by weight, and other monomer compounds (C) 0 to 9
It is obtained by graft polymerization of 4% by weight (the total of (A), (B) and (C) is 100% by weight), and the grafting efficiency is 30% or more. And

【０００５】上記「天然ゴム」は、特に限定されない
が、市販のラテックス等が好ましく用いられる。また、
「エポキシ化天然ゴム」は過酸化水素、過酸等のエポキ
シ化剤により天然ゴムにエポキシ基を導入したものであ
るが、特に限定されない。[0005] The "natural rubber" is not particularly limited, but commercially available latex and the like are preferably used. Also,
The “epoxidized natural rubber” is obtained by introducing an epoxy group into a natural rubber with an epoxidizing agent such as hydrogen peroxide or peracid, but is not particularly limited.

【０００６】上記「天然ゴム及び／又はエポキシ化天然
ゴムからなるゴム状重合体（Ａ）」の使用量は１〜９５
重量％の範囲であり、より好ましくは、２０〜８０重量
％の範囲で、更に好ましくは３０〜７０重量％の範囲で
用いられる。使用量が１重量％未満では、成形体の強度
の改善が見られず、９５重量％を越えると組成物の相溶
性が悪化する。The amount of the "rubber-like polymer (A) comprising natural rubber and / or epoxidized natural rubber" is from 1 to 95.
%, More preferably from 20 to 80% by weight, even more preferably from 30 to 70% by weight. If the amount is less than 1% by weight, no improvement in the strength of the molded body is observed, and if it exceeds 95% by weight, the compatibility of the composition deteriorates.

【０００７】上記「カルボキシル基含有単量体」として
は、アクリル酸、メタクリル酸、マレイン酸、無水マレ
イン酸、イタコン酸、無水イタコン酸、フマル酸等が挙
げられる。これらのうち、アクリル酸、メタクリル酸が
好ましく用いられる。上記「ヒドロキシル基含有単量
体」としては、２−ヒドロキシエチルアクリレート、２
−ヒドロキシエチルメタクリレート、２−ヒドロキシプ
ロピルアクリレート、２−ヒドロキシプロピルメタクリ
レート、４−ヒドロキシブチルアクリレート、ｎ−ヒド
ロキシエチルアクリルアミド等が挙げられる。The above-mentioned "carboxyl group-containing monomer" includes acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid and the like. Of these, acrylic acid and methacrylic acid are preferably used. Examples of the “hydroxyl group-containing monomer” include 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, n-hydroxyethyl acrylamide and the like.

【０００８】上記「グリシジル基含有単量体」として
は、グリシジルアクリレート、グリシジルメタクリレー
ト、ビニルグリシジルエーテル等が挙げられる。上記
「アミド系単量体」としては、アクリルアミド、メタク
リルアミド、ｎ−メチロールアクリルアミド、ジアセト
ンアクリルアミド、エタクリルアミド、クロトンアミ
ド、イタコンアミド、メチルイタコンアミド、マレイン
酸モノアミド、メチレンジアクリルアミド等が挙げられ
る。The above-mentioned "glycidyl group-containing monomer" includes glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether and the like. Examples of the above-mentioned “amide monomer” include acrylamide, methacrylamide, n-methylolacrylamide, diacetoneacrylamide, ethacrylamide, crotonamide, itaconamide, methylitaconamide, maleic monoamide, methylenediacrylamide and the like.

【０００９】上記「アミノ基含有単量体」としては、ジ
メチルアミノエチルアクリレート、ジメチルアミノエチ
ルメタクリレート、ジエチルアミノエチルアクリレー
ト、ジエチルアミノエチルメタクリレート、β−アミノ
エチルビニルエーテル、ジメチルアミノエチルビニルエ
ーテル等が挙げられる。Examples of the "amino group-containing monomer" include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, β-aminoethyl vinyl ether, dimethylaminoethyl vinyl ether and the like.

【００１０】本第１発明において、単量体化合物（Ｂ）
の使用量は５〜９９重量％の範囲であり、より好ましく
は、２０〜８０重量％の範囲で、更に好ましくは３０〜
７０重量％の範囲で用いられる。使用量が５重量％未満
では、相溶性が悪化し、９９重量％を越えると、組成物
からなる成形体の強度の改善が見られない。In the first invention, the monomer compound (B)
Is in the range of 5 to 99% by weight, more preferably in the range of 20 to 80% by weight, and still more preferably 30 to 80% by weight.
It is used in the range of 70% by weight. If the amount used is less than 5% by weight, the compatibility deteriorates, and if it exceeds 99% by weight, no improvement in the strength of the molded article comprising the composition is observed.

【００１１】本第１発明において、ゴム状重合体（Ａ）
のグラフト重合に使用し得る「他の単量体化合物
（Ｃ）」としては、上記（Ｂ）に示す単量体化合物以外
の単量体化合物であれば良く、スチレン、α−メチルス
チレン、４−メトキシスチレン、４−エトキシスチレ
ン、ジビニルベンゼン、１−ビニルナフタレン、２−ビ
ニルピリジン、アクリロニトリル、メタクリロニトリ
ル、クロトンニトリル、２−シアノエチルアクリレー
ト、２−シアノエチルメタクリレート、２−シアノプロ
ピルアクリレート、２−シアノプロピルメタクリレー
ト、３−シアノプロピルアクリレート、３−シアノプロ
ピルメタクリレート、メチルメタクリレート、ブタジエ
ン、イソプレン等が挙げられる。これらのうち、スチレ
ン、メチルメタクリレートが好ましく用いられる。ま
た、この単量体化合物の使用量は０〜９４重量％、好ま
しくは０〜８０重量％、更に好ましくは０〜６０重量％
である。In the first invention, the rubbery polymer (A)
As the "other monomer compound (C)" which can be used for the graft polymerization of the above, any monomer compound other than the monomer compound shown in the above (B) may be used, and styrene, α-methylstyrene, -Methoxystyrene, 4-ethoxystyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylpyridine, acrylonitrile, methacrylonitrile, crotononitrile, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, 2-cyanopropyl acrylate, 2-cyano Examples include propyl methacrylate, 3-cyanopropyl acrylate, 3-cyanopropyl methacrylate, methyl methacrylate, butadiene, isoprene and the like. Of these, styrene and methyl methacrylate are preferably used. The amount of the monomer compound used is 0 to 94% by weight, preferably 0 to 80% by weight, more preferably 0 to 60% by weight.
It is.

【００１２】本第１発明において、ゴム重合体（Ａ）に
対するグラフト効率は、３０％以上であり、より好まし
くは５０％以上、更に好ましくは６０％以上である。こ
れが３０％未満の場合は、十分な界面強度を得られない
ため好ましくない。尚、このグラフト効率の測定方法
は、実施例に示す。In the first invention, the grafting efficiency to the rubber polymer (A) is at least 30%, preferably at least 50%, more preferably at least 60%. If it is less than 30%, it is not preferable because sufficient interfacial strength cannot be obtained. The method for measuring the graft efficiency is described in Examples.

【００１３】本第１発明において、ゴム状重合体（Ａ）
のグラフト重合方法としては乳化重合、溶液重合、塊状
重合、懸濁重合等が挙げられるが、これらのうちで乳化
重合が好ましく用いられる。In the first invention, the rubbery polymer (A)
Examples of the graft polymerization method include emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization. Of these, emulsion polymerization is preferably used.

【００１４】本第１発明において、ゴム状重合体（Ａ）
を乳化重合する際には、重合開始剤、連鎖移動剤（分子
量調節剤）、乳化剤、水等が用いられる。尚、乳化重合
の際に用いるゴム状重合体（Ａ）、単量体化合物（Ｂ）
及び他の単量体化合物（Ｃ）は、ゴム状重合体（Ａ）全
量の存在下に、単量体化合物（Ｂ）、（Ｃ）を一括添加
して重合しても良く、分割もしくは連続添加して重合し
ても良い。また、これらを組み合わせた方法で、重合し
ても良い。更に、ゴム状重合体（Ａ）の全量又は一部
を、重合途中で添加して重合しても良い。In the first invention, the rubbery polymer (A)
When emulsion polymerization is carried out, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used. The rubber-like polymer (A) and the monomer compound (B) used in the emulsion polymerization
And the other monomer compound (C) may be polymerized by adding the monomer compounds (B) and (C) at once in the presence of the total amount of the rubbery polymer (A), It may be added and polymerized. Further, polymerization may be performed by a method combining these. Further, the whole or a part of the rubbery polymer (A) may be added during the polymerization to carry out the polymerization.

【００１５】重合開始剤としては、クメンハイドロパー
オキサイド、ジイソプロピルベンゼンハイドロパーオキ
サイド、パラメンタンハイドロパーオキサイド等の有機
ハイドロパーオキサイド類と含糖ピロリン酸処方、スル
ホキシレート処方等の還元剤との組み合わせによるレド
ックス系、あるいは過硫酸カリウムなどの過硫酸塩、ア
ゾビスイソブチロニトリル（ＡＩＢＮ）、ベンゾイルパ
ーオキサイド（ＢＰＯ）、ラウロイルパーオキサイド、
ｔ−ブチルパーオキシウレイト、ｔ−ブチルパーオキシ
モノカーボネート等の過酸化物が使用される。重合開始
剤は、重合に一括又は連続的に添加することができる。
更に、重合開始剤の使用量は、通常、単量体化合物全量
に対して、０．１〜１．５重量％、好ましくは０．２〜
０．７重量％である。As the polymerization initiator, a combination of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide or paramenthane hydroperoxide with a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. Redox system, or persulfates such as potassium persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauroyl peroxide,
Peroxides such as t-butyl peroxyureate and t-butyl peroxy monocarbonate are used. The polymerization initiator can be added to the polymerization all at once or continuously.
Further, the amount of the polymerization initiator used is usually 0.1 to 1.5% by weight, preferably 0.2 to 1.5% by weight, based on the total amount of the monomer compound.
0.7% by weight.

【００１６】連鎖移動剤は、公知のものが使用でき、例
えば、オクチルメルカプタン、ｎ−ドデシルメルカプタ
ン、ｔ−ドデシルメルカプタン、ｎ−ヘキシルメルカプ
タン、ｎ−ヘキサデシルメルカプタン、ｎ−テトラデシ
ルメルカプタン、ｔ−テトラデシルメルカプタン等のメ
ルカプタン類、テトラエチルチウラムスルフィド、四塩
化炭素、臭化エチレン、ペンタフェニルエタン等の炭化
水素塩類、テルペン類又はアクロレイン、メタクロレイ
ン、アリルアルコール、２−エチルヘキシルチオグリコ
ール、α−メチルスチレンのダイマー等が挙げられる。
これらの連鎖移動剤は、一種単独で使用することも、あ
るいは二種以上を組み合わせて使用することができる。
連鎖移動剤の使用量は、通常、単量体化合物全量に対し
て、０．０５〜２．０重量％である。As the chain transfer agent, known ones can be used. Mercaptans such as decyl mercaptan, tetraethylthiuram sulfide, carbon tetrachloride, ethylene bromide, hydrocarbon salts such as pentaphenylethane, terpenes or acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycol, α-methyl styrene And dimers.
These chain transfer agents can be used alone or in combination of two or more.
The amount of the chain transfer agent is usually 0.05 to 2.0% by weight based on the total amount of the monomer compound.

【００１７】乳化重合の場合に使用する乳化剤は、公知
のものが使用でき、例えば、高級アルコールの硫酸エス
テル、ドデシルベンゼンスルホン酸ナトリウム等のアル
キルベンゼンスルホン酸塩等の脂肪族スルホン酸塩、ラ
ウリル硫酸ナトリウム等の高級脂肪族カルボン酸塩、リ
ン酸系等のアニオン系界面活性剤、ポリエチレングリコ
ールのアルキルエステル型、アルキルエーテル型等のノ
ニオン系界面活性剤が挙げられる。これらは、一種単独
で使用することも、あるいは二種以上を組み合わせて使
用することもできる。乳化剤の使用量は、通常、単量体
化合物全量に対して０．３〜５．０重量％である。As the emulsifier used in the emulsion polymerization, known emulsifiers can be used, for example, sulfuric acid esters of higher alcohols, aliphatic sulfonates such as alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and sodium lauryl sulfate. And higher anionic surfactants such as phosphoric acid type, alkyl ester type and alkyl ether type of polyethylene glycol. These can be used alone or in combination of two or more. The amount of the emulsifier used is usually 0.3 to 5.0% by weight based on the total amount of the monomer compound.

【００１８】また、乳化重合では、通常、凝固剤により
凝固して得られた粉末を水洗後、乾燥することによって
本発明の改質剤が得られる。この凝固剤としては、塩化
カルシウム、硫酸マグネシウム、塩化マグネシウム、塩
化ナトリウム等の無機塩や硫酸、塩酸等の酸を使用する
ことができる。In the emulsion polymerization, the powder obtained by coagulation with a coagulant is usually washed with water and dried to obtain the modifier of the present invention. As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride, and acids such as sulfuric acid and hydrochloric acid can be used.

【００１９】本第２発明の生分解性ポリマー組成物は、
天然物系生分解性ポリマー、微生物合成系生分解性ポリ
マー及び化学合成系生分解性ポリマーの群から選ばれる
少なくとも一種の生分解性ポリマー、並びに本第１発明
の生分解性ポリマー改質剤を含有することを特徴とす
る。[0019] The biodegradable polymer composition of the second invention comprises:
At least one biodegradable polymer selected from the group consisting of a natural product-based biodegradable polymer, a microorganism-synthesized biodegradable polymer and a chemically synthesized biodegradable polymer, and the biodegradable polymer modifier of the first invention. It is characterized by containing.

【００２０】上記「天然物系生分解性ポリマー」として
は、キトサン、リグニン、デンプン、ニトロセルロー
ス、アセチルセルロース、グラフト化セルロース等が挙
げられる。これらのうちでデンプンが好ましく用いられ
る。上記「微生物合成系生分解性ポリマー」としては、
微生物貯蔵物質であるポリヒドロキシブチレート（ＰＨ
Ｂ）やその誘導体（ヒドロキシバリレート（ＰＨＶ）の
共重合体等）等が挙げられる。これらのうちでＰＨＢ／
ＰＨＶ共重合体が好ましく用いられる。上記「化学合成
系生分解性ポリマー」としては、ポリ乳酸、ポリカプロ
ラクトン（ＰＣＬ）、ポリグリコール酸等の脂肪酸ポリ
エステルや脂肪族ポリエステルアミド共重合体（ＣＰＡ
Ｅ）、ポリビニルアルコール（ＰＶＡ）等が挙げられ
る。これらのうちでポリ乳酸、ポリカプロラクトン等が
好ましく用いられる。Examples of the above-mentioned "natural product-based biodegradable polymer" include chitosan, lignin, starch, nitrocellulose, acetylcellulose, and grafted cellulose. Of these, starch is preferably used. As the above "microbial synthetic biodegradable polymer",
Microbial storage substance polyhydroxybutyrate (PH
B) and derivatives thereof (such as a copolymer of hydroxyvalerate (PHV)). PHB /
PHV copolymers are preferably used. Examples of the “synthetic biodegradable polymer” include fatty acid polyesters such as polylactic acid, polycaprolactone (PCL), and polyglycolic acid, and aliphatic polyesteramide copolymers (CPA).
E), polyvinyl alcohol (PVA) and the like. Among these, polylactic acid, polycaprolactone and the like are preferably used.

【００２１】上記生分解性ポリマーと上記生分解性ポリ
マー改質剤の配合割合については、第３発明に示すよう
に、生分解性ポリマー１００重量部に対して、上記生分
解性ポリマー改質剤を０．１〜７０重量部の範囲で含有
させ、より好ましくは１〜５０重量部の範囲で、更に好
ましくは５〜３０重量部の範囲で含有するものである。
０．１重量部未満では組成物からなる成形体の強度に改
善が見られず、７０重量部を越えると生分解性が悪化す
る。As to the mixing ratio of the biodegradable polymer and the biodegradable polymer modifier, as shown in the third invention, the biodegradable polymer modifier is added to 100 parts by weight of the biodegradable polymer. Is contained in the range of 0.1 to 70 parts by weight, more preferably in the range of 1 to 50 parts by weight, and still more preferably in the range of 5 to 30 parts by weight.
If the amount is less than 0.1 part by weight, no improvement is observed in the strength of the molded article made of the composition, and if it exceeds 70 parts by weight, the biodegradability deteriorates.

【００２２】本発明の生分解性ポリマー組成物は、通常
の混練り装置、例えば、ラバーミル、ブラベンダーミキ
サー、バンバリーミキサー、加圧ニーダー等を使用して
製造することができる。混練りに際しては、複数成分を
一括混練りしても良く、また任意の成分を混練りした
後、残りの成分を添加し、混練りする多段分割混練り法
を採用することもできる。The biodegradable polymer composition of the present invention can be produced by using a usual kneading apparatus, for example, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader and the like. At the time of kneading, a plurality of components may be kneaded at once, or a multi-stage kneading method of kneading arbitrary components, adding the remaining components, and kneading may be employed.

【００２３】本発明の生分解性ポリマー組成物からなる
成形品に所望の性質を付与するために、例えば、耐光性
を付与する紫外線安定剤、カーボンブラック等、またイ
ンフレート成形用に通常配合される殺菌剤、酸化防止
剤、充填剤、安定剤、可塑剤、着色剤等を配合すること
もできる。In order to impart desired properties to a molded article made of the biodegradable polymer composition of the present invention, for example, an ultraviolet stabilizer for imparting light resistance, carbon black, etc., which are usually compounded for inflation molding. Fungicides, antioxidants, fillers, stabilizers, plasticizers, coloring agents, and the like.

【００２４】[0024]

【発明の実施の形態】以下に、実施例を挙げて本発明を
具体的に説明するが、本発明はこれらの実施例に限定さ
れるものではない。尚、実施例及び比較例において、部
及び％は特に断らない限り重量基準である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, parts and percentages are by weight unless otherwise specified.

【００２５】評価方法 本実施例においては、以下に示す各種評価方法を適用し
た。 （１）引張強度試験 ＡＳＴＭ Ｄ６３８に準じて行った。Evaluation Methods In this example, the following various evaluation methods were applied. (1) Tensile strength test A tensile strength test was performed according to ASTM D638.

【００２６】（２）伸び試験 ＡＳＴＭ Ｄ６３８に準じて行った。(2) Elongation test The elongation test was carried out according to ASTM D638.

【００２７】（３）生分解性試験 土壌中に３年間放置した後の重量保持率を求めた。(3) Biodegradability test The weight retention rate after standing in soil for 3 years was determined.

【００２８】（４）グラフト効率 グラフト重合体の一定量ｘ（ｇ）をアセトン中に投入
し、振とう機で２時間振とうし、遊離の共重合体を溶解
させた。遠心分離器を用いてこの溶液を２３，０００ｒ
ｐｍで３０分間遠心分離し、不溶分を得た。次に、真空
乾燥機を用いて１２０℃で１時間乾燥し、不溶分ｙ
（ｇ）を得た。次式によりグラフト効率を算出した。 グラフト効率（％）＝〔ｙ−ｘ×グラフト重合体中のゴ
ム分率〕／〔ｘ−ｘ×グラフト重合体中のゴム分率〕×
１００(4) Graft Efficiency A fixed amount x (g) of the graft polymer was put into acetone and shaken with a shaker for 2 hours to dissolve the free copolymer. This solution was centrifuged at 23,000 rpm.
After centrifugation at pm for 30 minutes, an insoluble matter was obtained. Next, it is dried at 120 ° C. for 1 hour using a vacuum drier,
(G) was obtained. The graft efficiency was calculated by the following equation. Graft efficiency (%) = [yx × rubber fraction in graft polymer] / [xx × rubber fraction in graft polymer] ×
100

【００２９】実施例１ 固形分３０％の天然ゴムラテックス（商品名：「エレフ
ァント」）１００ｇに、メタクリル酸５ｇ及び過硫酸カ
リウム０．０１ｇを添加し、７０℃で３時間重合した。
得られたラテックスにアルコールを加え凝固し、不純物
を取り除き、改質剤を得た。尚、この改質剤のグラフト
効率は、８０重量％である。この改質剤３０ｇをポリ乳
酸１００ｇに混合し、押出機で１５０℃で造粒し、生分
解性ポリマー組成物を得た。１５０℃の射出成形機によ
り成形後、試験サンプルを作製し、上記評価を行った。Example 1 5 g of methacrylic acid and 0.01 g of potassium persulfate were added to 100 g of natural rubber latex (trade name: "Elephant") having a solid content of 30%, and polymerized at 70 ° C for 3 hours.
Alcohol was added to the obtained latex for coagulation, impurities were removed, and a modifier was obtained. The grafting efficiency of this modifier is 80% by weight. 30 g of this modifier was mixed with 100 g of polylactic acid and granulated at 150 ° C. with an extruder to obtain a biodegradable polymer composition. After molding with a 150 ° C. injection molding machine, test samples were prepared and evaluated as described above.

【００３０】比較例１ 実施例１で用いたポリ乳酸を単独で試験用サンプルを作
製し、同様の評価を行った。Comparative Example 1 A test sample was prepared using the polylactic acid used in Example 1 alone, and the same evaluation was performed.

【００３１】実施例２ 上記改質剤３０ｇをポリカプロラクトン１００ｇに混合
し、押出機で造粒し、生分解性ポリマー組成物を得た。
上記と同様にして、試験サンプルを作製して評価を行っ
た。Example 2 30 g of the above modifier was mixed with 100 g of polycaprolactone and granulated with an extruder to obtain a biodegradable polymer composition.
A test sample was prepared and evaluated in the same manner as described above.

【００３２】比較例２ 実施例２で用いたポリカプロラクトンを単独で試験用サ
ンプルを作製し、同様の評価を行った。Comparative Example 2 A test sample was prepared using only the polycaprolactone used in Example 2 and the same evaluation was performed.

【００３３】実施例１及び２、並びに比較例１及び２で
得た試験用サンプル（Ｎｏ．１〜４）の評価結果を表１
に示す。Table 1 shows the evaluation results of the test samples (Nos. 1 to 4) obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
Shown in

【００３４】[0034]

【表１】 [Table 1]

【００３５】表１の結果によれば、改質後のポリ乳酸系
生分解性ポリマー組成物（実施例１）の場合、改質前の
ポリ乳酸（比較例１）と比べると、引張強度が６５０Ｋ
ｇ／ｃｍ２と約８％向上し、伸びは５０倍という著しい
向上をみせ、更に生分解性も２０％も向上した。また、
改質後のポリカプロラクトン系生分解性ポリマー組成物
（実施例２）の場合、改質前のポリカプロラクトン（比
較例２）と比べると、引張強度が２５０Ｋｇ／ｃｍ２と
２５％も向上し、伸びも４０％の向上をみせ、更に生分
解性も２５％も向上した。以上より、改質後の生分解性
組成物（実施例１、２）は、生分解性ポリマーの改質剤
が含有されない改質前の生分解性組成物（比較例１、
２）と比べると、引張強度、伸び及び生分解性の全ての
点において優れた結果を示した。従って、本実施例１、
２においては、改質剤の効果が発揮されていることを示
した。According to the results shown in Table 1, the modified polylactic acid-based biodegradable polymer composition (Example 1) has a lower tensile strength than the polylactic acid before modification (Comparative Example 1). 650K
g / cm2, which is about 8%, the elongation is remarkably improved by 50 times, and the biodegradability is also improved by 20%. Also,
In the case of the modified polycaprolactone-based biodegradable polymer composition (Example 2), the tensile strength is improved to 250 kg / cm 2, 25% as compared with the unmodified polycaprolactone (Comparative Example 2), and the elongation is improved. Showed a 40% improvement, and the biodegradability also improved by 25%. As described above, the biodegradable composition after modification (Examples 1 and 2) is a biodegradable composition before modification (Comparative Example 1, which does not contain a biodegradable polymer modifier).
As compared with 2), excellent results were shown in all points of tensile strength, elongation and biodegradability. Therefore, the first embodiment,
In No. 2, it was shown that the effect of the modifier was exhibited.

【００３６】[0036]

【発明の効果】本発明の生分解性ポリマー改質剤は自然
界に豊富に存在する天然ゴムを既存の生分解性ポリマー
と相溶しやすくなるように変性するもので、これを用い
た生分解性樹脂組成物は、強度及び伸びに優れ、更に生
分解性も良好である。しかも、本発明の生分解性ポリマ
ー改質剤は、従来の生分解性樹脂に比べて安価な生分解
性樹脂組成物、ひいてはその成形品を提供することがで
きる。また、本発明の生分解性ポリマー組成物は、上記
の優れた性能を備える改質剤を含有するので、強度、伸
び及び生分解性に優れる成形品を提供することができ
る。以上より、本発明の生分解性ポリマー改質剤及び本
発明の生分解性ポリマー組成物は、地球環境及び生物環
境等の破壊を低減させる材料として、広範囲な分野に応
用できる。The biodegradable polymer modifier of the present invention modifies natural rubber, which is abundant in nature, so that it is easily compatible with existing biodegradable polymers. The water-soluble resin composition has excellent strength and elongation, and also has good biodegradability. In addition, the biodegradable polymer modifier of the present invention can provide a biodegradable resin composition which is less expensive than conventional biodegradable resins, and can provide a molded article thereof. Further, since the biodegradable polymer composition of the present invention contains the modifier having the above-described excellent performance, a molded article having excellent strength, elongation and biodegradability can be provided. As described above, the biodegradable polymer modifier of the present invention and the biodegradable polymer composition of the present invention can be applied to a wide range of fields as a material for reducing the destruction of the global environment and biological environment.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ａ０１Ｇ 9/14 ＺＡＢ Ａ０１Ｇ 9/14 ＺＡＢＳ 13/02 ＺＡＢ 13/02 ＺＡＢＤ Ｃ０８Ｌ 51/04 Ｃ０８Ｌ 51/04 101/16 101/16 Ｆターム(参考） 2B024 DB01 2B027 NC02 NC24 ND01 ND03 2B029 EB02 EC06 EC09 EC20 RA03 4J002 AB02X AB04X AB05X BE02X BN01X BN02W CF18X CF19X CH03X CL08X GA01 GG01 GG02 4J026 AA06 AC18 AC24 AC32 BA04 BA05 BA06 BA07 BA16 BA25 BA27 BA29 BA30 BA31 BA32 BA34 BA35 BA37 BA38 BA46 BA47 BB01 BB03 CA03 DB02 DB03 DB04 DB05 DB12 DB14 DB15 DB16 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) A01G 9/14 ZAB A01G 9/14 ZABS 13/02 ZAB 13/02 ZABD C08L 51/04 C08L 51/04 101 / 16 101/16 F term (reference) 2B024 DB01 2B027 NC02 NC24 ND01 ND03 2B029 EB02 EC06 EC09 EC20 RA03 4J002 AB02X AB04X AB05X BE02X BN01X BN02W CF18X CF19X CH03X CL08X GA01 GG01 GG02 4J026 BA04AC04 BA30 BA31 BA32 BA34 BA35 BA37 BA38 BA46 BA47 BB01 BB03 CA03 DB02 DB03 DB04 DB05 DB12 DB14 DB15 DB16

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 天然ゴム及び／又はエポキシ化天然ゴム
からなるゴム状重合体（Ａ）１〜９５重量％の存在下
に、カルボキシル基含有単量体、ヒドロキシル基含有単
量体、グリシジル基含有単量体、アミド系単量体及びア
ミノ基含有単量体の群から選ばれる少なくとも一種の単
量体化合物（Ｂ）５〜９９重量％、並びに他の単量体化
合物（Ｃ）０〜９４重量％（但し、上記（Ａ）、上記
（Ｂ）及び上記（Ｃ）の合計が１００重量％である。）
をグラフト重合して得られ、且つグラフト効率が３０％
以上であることを特徴とする生分解性ポリマー改質剤。1. A carboxyl group-containing monomer, a hydroxyl group-containing monomer and a glycidyl group-containing monomer in the presence of 1 to 95% by weight of a rubbery polymer (A) composed of natural rubber and / or epoxidized natural rubber. 5 to 99% by weight of at least one monomer compound (B) selected from the group consisting of a monomer, an amide monomer and an amino group-containing monomer, and from 0 to 94 of another monomer compound (C). % By weight (provided that the sum of (A), (B) and (C) is 100% by weight)
Is obtained by graft polymerization, and the grafting efficiency is 30%.
A biodegradable polymer modifier characterized by the above. 【請求項２】 天然物系生分解性ポリマー、微生物合成
系生分解性ポリマー及び化学合成系生分解性ポリマーの
群から選ばれる少なくとも一種の生分解性ポリマー、並
びに請求項１記載の生分解性ポリマー改質剤を含有する
ことを特徴とする生分解性ポリマー組成物。2. The biodegradable polymer according to claim 1, wherein the biodegradable polymer is at least one selected from the group consisting of a natural biodegradable polymer, a microbial biodegradable polymer and a chemically synthesized biodegradable polymer. A biodegradable polymer composition comprising a polymer modifier. 【請求項３】 天然物系生分解性ポリマー、微生物合成
系生分解性ポリマー及び化学合成系生分解性ポリマーの
群から選ばれる少なくとも一種の生分解性ポリマー１０
０重量部に対して、上記生分解性ポリマー改質剤を０．
１〜７０重量部含有してなる請求項２記載の生分解性ポ
リマー組成物。3. A biodegradable polymer selected from the group consisting of a biodegradable polymer of a natural product type, a biodegradable polymer of a microbial synthesis type, and a biodegradable polymer of a chemical synthesis type.
The biodegradable polymer modifier was added in an amount of 0.1 part by weight.
3. The biodegradable polymer composition according to claim 2, comprising 1 to 70 parts by weight.
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