JP2007302748A - New biodegradable compatibilizer and resin composition comprising the same - Google Patents
New biodegradable compatibilizer and resin composition comprising the same Download PDFInfo
- Publication number
- JP2007302748A JP2007302748A JP2006130718A JP2006130718A JP2007302748A JP 2007302748 A JP2007302748 A JP 2007302748A JP 2006130718 A JP2006130718 A JP 2006130718A JP 2006130718 A JP2006130718 A JP 2006130718A JP 2007302748 A JP2007302748 A JP 2007302748A
- Authority
- JP
- Japan
- Prior art keywords
- block chain
- aliphatic polyester
- vinyl polymer
- polyester block
- meth
- 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.)
- Granted
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 24
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 22
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 12
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- 239000000178 monomer Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 150000002596 lactones Chemical class 0.000 claims description 16
- 229920000704 biodegradable plastic Polymers 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 125000002348 vinylic group Chemical group 0.000 abstract 4
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- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 5
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- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
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- 229920001610 polycaprolactone Polymers 0.000 description 5
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- 238000010791 quenching Methods 0.000 description 5
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- 238000009864 tensile test Methods 0.000 description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
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- 229920002961 polybutylene succinate Polymers 0.000 description 4
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- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
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- 238000004108 freeze drying Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 229960000834 vinyl ether Drugs 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
本発明は、側鎖にエポキシ基及び脂肪族ポリエステルブロック鎖を有するビニル系重合体及びこのビニル系重合体で構成された相溶化剤に関する。 The present invention relates to a vinyl polymer having an epoxy group and an aliphatic polyester block chain in a side chain, and a compatibilizing agent composed of the vinyl polymer.
農業分野では、塩化ビニル系のマルチフィルムや園芸用被覆資材などが使用されていたが、焼却によるダイオキシンの発生が問題となっている。そこで、近年、塩化ビニル系材料の代替物として、土壌中で水と二酸化炭素とに分解する生分解性プラスチックが注目されている。生分解性プラスチックには、セルロース、デンプン、ポリヒドロキシ酪酸などの天然系多糖類又は樹脂、脂肪族ポリエステル、芳香族ポリエステル、ポリエステルカーボネート、ポリビニルアルコール、ポリウレタンなどの合成樹脂が含まれる。これらの生分解性プラスチックの中でも、機械的特性及び生分解性に優れ、人工的に合成できる点から、ポリカプロラクトン、ポリブチレンサクシネート、ポリ乳酸などの脂肪族ポリエステル系樹脂が汎用されている。 In the agricultural field, vinyl chloride-based multifilms and horticultural coating materials have been used, but the generation of dioxins due to incineration has become a problem. Thus, in recent years, biodegradable plastics that decompose into water and carbon dioxide in soil have attracted attention as an alternative to vinyl chloride materials. Biodegradable plastics include natural polysaccharides or resins such as cellulose, starch, and polyhydroxybutyric acid, and synthetic resins such as aliphatic polyesters, aromatic polyesters, polyester carbonates, polyvinyl alcohols, and polyurethanes. Among these biodegradable plastics, aliphatic polyester resins such as polycaprolactone, polybutylene succinate, and polylactic acid are widely used because they are excellent in mechanical properties and biodegradability and can be artificially synthesized.
これらのうち、ポリカプロラクトンは、ポリエチレンやポリプロピレン並みの機械的強度を有し、分解性に優れているが、融点が６０℃と低く、透明性に劣る。また、ポリブチレンサクシネートは、ポリプロピレンやポリエチレンテレフタレート並みの機械的強度を有し、分解性にも優れているが、融点が１１４℃と比較的低く、透明性に劣る。さらに、ポリ乳酸は、硬質で透明性も高く、融点も１８０℃と比較的高いが、土中での分解性が低く、硬くて脆い。このように、生分解性プラスチックは単独では、ニーズに応じた物性を得るのが困難であるため、生分解性プラスチック同士をブレンドする試みが提案されている。 Of these, polycaprolactone has the same mechanical strength as polyethylene and polypropylene and is excellent in decomposability, but has a melting point as low as 60 ° C. and is inferior in transparency. Polybutylene succinate has mechanical strength comparable to that of polypropylene and polyethylene terephthalate and is excellent in decomposability, but has a relatively low melting point of 114 ° C. and poor transparency. Furthermore, polylactic acid is hard and highly transparent, and has a relatively high melting point of 180 ° C., but has low degradability in the soil and is hard and brittle. Thus, since it is difficult to obtain physical properties according to the needs of a single biodegradable plastic, attempts to blend biodegradable plastics have been proposed.
ポリマーのブレンドにおいては、通常、分子レベルでの相溶ができず、マイクロメートルオーダー以上に相分離（マクロ相分離）して非相溶系となる。このような非相溶系の状態では、ポリマー間の界面接着力が弱く、優れた力学的特性や安定したモルフォロジーを示さない。そこで、この系への両方のポリマーになじみ易い共重合体などを、相溶化剤として添加することにより、両ポリマーの相溶性を向上させることが行われている。 In polymer blends, it is usually impossible to achieve compatibility at the molecular level, and phase separation (macrophase separation) of the order of micrometers or more becomes an incompatible system. In such an incompatible state, the interfacial adhesive force between the polymers is weak, and excellent mechanical properties and stable morphology are not exhibited. Therefore, the compatibility of both polymers is improved by adding, as a compatibilizing agent, a copolymer that is compatible with both polymers in this system.
相溶化剤には、非反応性相溶化剤と反応性相溶化剤とが含まれる。一般的に汎用されるのは非反応性相溶化剤であるが、添加量が比較的多く必要であり、ポリマーアロイの物性が変化し、経済的にも不利である。反応性相溶化剤は、官能基がポリマーに化学反応するため、少量の添加で効果が大きいが、相溶性が高く、生分解性も有する相溶化剤は知られていない。特に、相溶化剤自身も生分解性を有していれば、生分解性プラスチックのブレンドに限定されず、その用途が広がるため有用である。 The compatibilizing agent includes a non-reactive compatibilizing agent and a reactive compatibilizing agent. Generally used are non-reactive compatibilizers, but they need to be added in a relatively large amount, which changes the physical properties of the polymer alloy and is also disadvantageous economically. The reactive compatibilizing agent is highly effective when added in a small amount because the functional group chemically reacts with the polymer, but no compatibilizing agent having high compatibility and biodegradability is known. In particular, if the compatibilizer itself has biodegradability, it is not limited to blends of biodegradable plastics, and is useful because its use is widened.
なお、特開平８−７３５７７号公報（特許文献１）には、塗料、接着剤、成型材料又はその改質剤として、水酸基及び／又はカルボキシル基を有するビニルモノマーを開始剤として、エポキシドと環状酸無水物とを開環共重合させて得られるポリエステル系マクロモノマーが開示されている。この文献には、このポリエステル系マクロモノマーが、数平均分子量３００〜１０００００で、ガラス転移温度−７０〜１００℃であり、他の重合性ビニルモノマーと共重合可能であることが記載されている。 In JP-A-8-73577 (Patent Document 1), as a coating material, an adhesive, a molding material, or a modifier thereof, a vinyl monomer having a hydroxyl group and / or a carboxyl group is used as an initiator, and an epoxide and a cyclic acid. A polyester-based macromonomer obtained by ring-opening copolymerization with an anhydride is disclosed. This document describes that the polyester-based macromonomer has a number average molecular weight of 300 to 100,000, a glass transition temperature of −70 to 100 ° C., and can be copolymerized with other polymerizable vinyl monomers.
しかし、エポキシ基と脂肪族ポリエステル基との組み合わせについては記載されておらず、このマクロモノマーの生分解性や相溶化剤としての作用についても記載されていない。
従って、本発明の目的は、生分解性を有し、かつ異種のポリマーの相溶性を向上できるビニル重合体及び相溶化剤を提供することにある。 Accordingly, an object of the present invention is to provide a vinyl polymer and a compatibilizing agent that are biodegradable and can improve the compatibility of different polymers.
本発明の他の目的は、異種のポリマーを相溶化でき、ポリマーアロイの機械的特性を向上できる相溶化剤を提供することにある。 Another object of the present invention is to provide a compatibilizing agent capable of compatibilizing different polymers and improving the mechanical properties of the polymer alloy.
本発明の他の目的は、生分解性プラスチックを含んでいても、実用性の高いポリマーアロイを提供することにある。 Another object of the present invention is to provide a highly practical polymer alloy even if it contains a biodegradable plastic.
本発明者らは、前記課題を達成するため鋭意検討した結果、ビニル系重合体の側鎖にエポキシ基及び脂肪族ポリエステルブロック鎖を導入することにより、生分解性を有するとともに、異種のポリマーの相溶性を向上できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have introduced an epoxy group and an aliphatic polyester block chain into the side chain of the vinyl polymer, thereby having biodegradability and different types of polymers. The present inventors have found that the compatibility can be improved and completed the present invention.
すなわち、本発明のビニル系重合体は、側鎖にエポキシ基及び脂肪族ポリエステルブロック鎖を有する。前記脂肪族ポリエステルブロック鎖は、Ｃ３−１２ラクトン類が開環重合したポリラクトンブロック鎖であってもよく、その重量平均分子量は、１０００〜５０×１０４程度であってもよい。エポキシ基と脂肪族ポリエステルブロック鎖との割合（モル比）は、前者／後者＝５／１〜１００００／１程度である。 That is, the vinyl polymer of the present invention has an epoxy group and an aliphatic polyester block chain in the side chain. The aliphatic polyester block chain may be a polylactone block chain obtained by ring-opening polymerization of C 3-12 lactones, and the weight average molecular weight may be about 1000 to 50 × 10 4 . The ratio (molar ratio) between the epoxy group and the aliphatic polyester block chain is about the former / the latter = 5/1 to 10000/1.
本発明のビニル系重合体は、グリシジル（メタ）アクリレートと、脂肪族ポリエステルブロック鎖を有するアクリル系マクロモノマーとを重合成分とするアクリル系グラフト共重合体であってもよい。前記アクリル系マクロモノマーは、ヒドロキシ基を有するアクリル系モノマーに、Ｃ４−１０ラクトン類を開環重合させたマクロモノマーであってもよい。グリシジル（メタ）アクリレートと、アクリル系マクロモノマーとの割合（モル比）は、前者／後者＝１０／１〜５０００／１程度である。本発明のビニル系重合体の重量平均分子量は１００００〜５００×１０４程度であってもよい。本発明のビニル系重合体は、生分解性を有している。 The vinyl polymer of the present invention may be an acrylic graft copolymer containing glycidyl (meth) acrylate and an acrylic macromonomer having an aliphatic polyester block chain as polymerization components. The acrylic macromonomer may be a macromonomer obtained by ring-opening polymerization of a C 4-10 lactone to an acrylic monomer having a hydroxy group. The ratio (molar ratio) between glycidyl (meth) acrylate and acrylic macromonomer is about the former / the latter = 10/1 to 5000/1. The vinyl polymer of the present invention may have a weight average molecular weight of about 10,000 to 500 × 10 4 . The vinyl polymer of the present invention has biodegradability.
本発明には、前記ビニル系重合体で構成された相溶化剤も含まれる。 The present invention also includes a compatibilizing agent composed of the vinyl polymer.
さらに、本発明には、複数のポリマーと、前記相溶化剤とで構成された樹脂組成物も含まれる。この樹脂組成物は、複数のポリマーとして、少なくとも生分解性プラスチックを含んでいてもよい。 Furthermore, the present invention includes a resin composition composed of a plurality of polymers and the compatibilizing agent. This resin composition may contain at least a biodegradable plastic as a plurality of polymers.
本発明では、ビニル系重合体の側鎖にエポキシ基及び脂肪族ポリエステルブロック鎖が導入されているため、生分解性を有するとともに、異種のポリマーの相溶性を向上できる。従って、相溶化剤として利用すると、異種のポリマーの相溶性に優れ、ポリマーアロイの機械的特性を向上できる。特に、生分解性プラスチック（例えば、脂肪族ポリエステルなど）を含んでいても、実用性の高いポリマーアロイが得られる。 In the present invention, an epoxy group and an aliphatic polyester block chain are introduced into the side chain of the vinyl polymer, so that it has biodegradability and can improve the compatibility of different polymers. Therefore, when used as a compatibilizing agent, the compatibility of different polymers is excellent, and the mechanical properties of the polymer alloy can be improved. In particular, even when a biodegradable plastic (for example, aliphatic polyester) is included, a highly practical polymer alloy can be obtained.
［ビニル系重合体］
本発明のビニル系重合体は、側鎖にエポキシ基及び脂肪族ポリエステルブロック鎖を有するビニル系重合体である。骨格となるビニル系重合体には、アクリル系重合体、ビニルエーテル系重合体、酢酸ビニル系重合体、ビニルアルコール系重合体などが含まれるが、エポキシ基及び脂肪族ポリエステルブロック鎖を導入し易い点などから、アクリル系重合体が好ましい。
[Vinyl polymer]
The vinyl polymer of the present invention is a vinyl polymer having an epoxy group and an aliphatic polyester block chain in the side chain. The vinyl polymer used as the skeleton includes acrylic polymers, vinyl ether polymers, vinyl acetate polymers, vinyl alcohol polymers, etc., but it is easy to introduce epoxy groups and aliphatic polyester block chains. From the above, an acrylic polymer is preferable.
アクリル系重合体は、アクリル系モノマーを主要な重合成分とする重合体である。アクリル系モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル［（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、(メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルへキシルなどの（メタ）アクリル酸Ｃ１−２０アルキルエステルなど］、（メタ）アクリル酸シクロへキシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸ヒドロキシアルキルエステル［（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−クロロ−２−ヒドロキシブチル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸５，６−ジヒドロキシヘキシル等の（メタ）アクリル酸ヒドロキシＣ２−６アルキルエステルなど］、シアン化ビニル系モノマー［（メタ）アクリロニトリルなど］などが挙げられる。これらのアクリル系モノマーは、単独で又は二種以上組み合わせて使用できる。これらのアクリル系モノマーのうち、反応性基を有するアクリル系モノマー、例えば、（メタ）アクリル酸、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２−ヒドロキシエチルなどの（メタ）アクリル酸ヒドロキシＣ２−６アルキルエステルなどが好ましい。 The acrylic polymer is a polymer having an acrylic monomer as a main polymerization component. Examples of the acrylic monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylic acid octyl, (meth) acrylic acid C 1-20 alkyl ester such as 2-ethylhexyl acrylate, etc.], (meth) acrylic acid cyclohexyl, (meth) acrylic acid phenyl, ( Benzyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyalkyl ester (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro (meth) acrylate 2-hydroxybutyl, 2-hydroxybutyl (meth) acrylate, (meta Include acrylic acid 6-hydroxyhexyl, and the like (meth) acrylic acid 5,6-dihydroxy-hexyl (meth) acrylic acid hydroxyalkyl C 2-6 alkyl ester, a vinyl cyanide monomer [(meth) acrylonitrile, etc.] It is done. These acrylic monomers can be used alone or in combination of two or more. Among these acrylic monomers, acrylic monomers having a reactive group, for example, (meth) acrylic acid hydroxy C such as (meth) acrylic acid, (meth) acrylic acid glycidyl, (meth) acrylic acid 2-hydroxyethyl, etc. 2-6 alkyl esters and the like are preferable.
さらに、アクリル系重合体は、他の共重合可能なモノマーを重合成分として含んでいてもよい。共重合性モノマーとしては、例えば、オレフィン系モノマー（例えば、エチレン、プロピレン、１−ブテンなどのＣ２−６オレフィンなど）、芳香族ビニル系モノマー（スチレン、ビニルトルエン、α−メチルスチレンなど）、不飽和多価カルボン酸又はその酸無水物（例えば、マレイン酸、イタコン酸、シトラコン酸又はその酸無水物など）、イミド系モノマー［例えば、マレイミド、Ｎ−アルキルマレイミド（例えば、Ｎ−Ｃ１−４アルキルマレイミドなど）、Ｎ−シクロアルキルマレイミド（例えば、Ｎ−シクロヘキシルマレイミドなど）、Ｎ−アリールマレイミド（例えば、Ｎ−フェニルマレイミドなど）などのＮ−置換マレイミドなど］などが挙げられる。これらの共重合性モノマーも単独で又は二種以上組み合わせて使用できる。これらの共重合性モノマーの割合は、例えば、重合体中３モル％以下（例えば、０〜３０モル％）、好ましくは２０モル％以下（例えば、０．１〜２０モル％）、さらに好ましくは１０モル％以下（１〜１０モル％）程度である。 Further, the acrylic polymer may contain another copolymerizable monomer as a polymerization component. Examples of the copolymerizable monomer include olefin monomers (for example, C 2-6 olefins such as ethylene, propylene, and 1-butene), aromatic vinyl monomers (styrene, vinyl toluene, α-methylstyrene, and the like), Unsaturated polyvalent carboxylic acid or acid anhydride thereof (for example, maleic acid, itaconic acid, citraconic acid or acid anhydride thereof), imide monomer [for example, maleimide, N-alkylmaleimide (for example, N-C 1- 4 alkylmaleimides, etc.), N-cycloalkylmaleimides (eg, N-cyclohexylmaleimides, etc.), N-arylmaleimides (eg, N-phenylmaleimides, etc.), etc.]. These copolymerizable monomers can also be used alone or in combination of two or more. The ratio of these copolymerizable monomers is, for example, 3 mol% or less (for example, 0 to 30 mol%), preferably 20 mol% or less (for example, 0.1 to 20 mol%), more preferably in the polymer. It is about 10 mol% or less (1-10 mol%).
さらに、このようなモノマーを重合成分とするビニル系重合体は、側鎖にエポキシ基及び脂肪族ポリエステルブロック鎖が導入されている。 Furthermore, an epoxy group and an aliphatic polyester block chain are introduced into the side chain of a vinyl polymer having such a monomer as a polymerization component.
エポキシ基は、３，４−エポキシシクロヘキシルなどの脂環式エポキシ基であってもよいが、通常、前記グリシジル（メタ）アクリレートやアリルグリシジルエーテルなどを共重合することにより、グリシジル基として導入される。 The epoxy group may be an alicyclic epoxy group such as 3,4-epoxycyclohexyl, but is usually introduced as a glycidyl group by copolymerizing the glycidyl (meth) acrylate or allyl glycidyl ether. .
脂肪族ポリエステルブロック鎖は、例えば、Ｃ３−１２脂肪族エステル単位（特にＣ３−１０脂肪族エステル単位）で構成されている。このような脂肪族ポリエステルブロックは、ジカルボン酸成分とジオール成分との重縮合により得られるポリエステルブロック、オキシカルボン酸の重縮合により得られるポリオキシカルボン酸ブロック、ラクトンの開環（付加）重合により得られるポリラクトンブロック、これらの成分を組み合わせて重合したポリエステルブロック（例えば、ジカルボン酸成分とジオール成分とオキシカルボン酸との重縮合により得られるポリエステル、オキシカルボン酸とラクトンとの重縮合により得られたポリエステルブロックなど）などが含まれる。脂肪族ポリエステルブロック鎖は、通常、（メタ）アクリル酸ヒドロキシアルキルエステルのヒドロキシル基に導入されている。 The aliphatic polyester block chain is composed of, for example, a C 3-12 aliphatic ester unit (particularly a C 3-10 aliphatic ester unit). Such an aliphatic polyester block is obtained by a polyester block obtained by polycondensation of a dicarboxylic acid component and a diol component, a polyoxycarboxylic acid block obtained by polycondensation of oxycarboxylic acid, or a ring-opening (addition) polymerization of a lactone. Polylactone block, polyester block polymerized by combining these components (for example, polyester obtained by polycondensation of dicarboxylic acid component, diol component and oxycarboxylic acid, obtained by polycondensation of oxycarboxylic acid and lactone) Polyester block, etc.). The aliphatic polyester block chain is usually introduced into the hydroxyl group of the (meth) acrylic acid hydroxyalkyl ester.
前記ポリエステルブロックにおいて、ジカルボン酸成分としては、例えば、シュウ酸、コハク酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸などのＣ２−１２脂肪族ジカルボン酸などが挙げられる。なお、これらのジカルボン酸成分は、反応性誘導体（例えば、酸無水物、メチルエステルなどのＣ１−３アルキルエステル、クロライドなどの酸ハライドなどのハロゲン化物など）であってもよい。これらのジカルボン酸成分は、単独で又は二種以上組み合わせて使用できる。これらのジカルボン酸成分のうち、シュウ酸、コハク酸、アジピン酸などのＣ２−６脂肪族カルボン酸が好ましい。 In the polyester block, as the dicarboxylic acid component, for example, oxalic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. C 2-12 aliphatic dicarboxylic acids such as dodecanedioic acid It is done. These dicarboxylic acid components may be reactive derivatives (eg, acid anhydrides, C 1-3 alkyl esters such as methyl esters, halides such as acid halides such as chloride, etc.). These dicarboxylic acid components can be used alone or in combination of two or more. Of these dicarboxylic acid components, C 2-6 aliphatic carboxylic acids such as oxalic acid, succinic acid, and adipic acid are preferred.
ジオール成分としては、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，３−ブタンジオール、ネオペンチルグリコール、ヘキサンジオール、オクタメチレングリコール、ドデカメチレングリコールなどの脂肪族Ｃ２−１２アルカンジオールなどが挙げられる。これらのジオール成分は、単独で又は二種以上組み合わせて使用できる。これらのジオール成分のうち、エチレングリコール、１，４−ブタンジオール、ネオペンチルグリコールなどの脂肪族Ｃ２−１０アルカンジオールが好ましい。 Examples of the diol component include aliphatic C such as ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octamethylene glycol, and dodecamethylene glycol. Examples include 2-12 alkanediol. These diol components can be used alone or in combination of two or more. Of these diol components, aliphatic C 2-10 alkanediols such as ethylene glycol, 1,4-butanediol, and neopentyl glycol are preferred.
前記ポリオキシカルボン酸において、オキシカルボン酸としては、例えば、グリコール酸、乳酸、リンゴ酸、オキシプロピオン酸、オキシ酪酸などのＣ２−１０オキシ脂肪族カルボン酸などが挙げられる。なお、これらのオキシカルボン酸も、前記反応性誘導体であってもよい。これらのオキシカルボン酸は、単独で又は二種以上組み合わせて使用できる。これらのオキシカルボン酸のうち、グリコール酸、乳酸、リンゴ酸、オキシ酪酸などのＣ２−６オキシ脂肪族カルボン酸が好ましい。 In the polyoxycarboxylic acid, examples of the oxycarboxylic acid include C 2-10 oxyaliphatic carboxylic acids such as glycolic acid, lactic acid, malic acid, oxypropionic acid, and oxybutyric acid. These oxycarboxylic acids may also be the reactive derivatives. These oxycarboxylic acids can be used alone or in combination of two or more. Of these oxycarboxylic acids, C 2-6 oxyaliphatic carboxylic acids such as glycolic acid, lactic acid, malic acid, and oxybutyric acid are preferred.
前記ラクトンにおいて、ラクトンとしては、例えば、プロピオラクトン（β−プロピオラクトンなど）、ブチロラクトン、バレロラクトン（δ−バレロラクトン、メチル化（δ−バレロラクトン）など）、カプロラクトン（ε−カプロラクトン、２−メチル−ε−カプロラクトン、４−メチル−ε−カプロラクトン、４，４’−ジメチル−ε−カプロラクトンなどのメチル化カプロラクトン（ε−カプロラクトンなど）など）などのＣ３−１２ラクトンが挙げられる。これらのラクトンは、単独で又は二種以上組み合わせて使用できる。これらのラクトンのうち、プロピオラクトン、カプロラクトン（例えば、ε−カプロラクトンなど）などのＣ４−１０ラクトン、特にＣ５−８ラクトンが好ましい。 In the lactone, examples of the lactone include propiolactone (such as β-propiolactone), butyrolactone, valerolactone (such as δ-valerolactone and methylation (δ-valerolactone)), caprolactone (ε-caprolactone, 2 C 3-12 lactones such as methylated caprolactone (such as ε-caprolactone) such as -methyl-ε-caprolactone, 4-methyl-ε-caprolactone, 4,4′-dimethyl-ε-caprolactone and the like. These lactones can be used alone or in combination of two or more. Among these lactones, C 4-10 lactones such as propiolactone and caprolactone (for example, ε-caprolactone, etc.), particularly C 5-8 lactones are preferable.
これらの脂肪族ポリエステルブロック鎖のうち、Ｃ２−６アルキレン単位を有するモノマーから得られたポリエステルが好ましく使用できる。具体例としては、ポリエチレンサクシネート、ポリブチレンサクシネート、ポリネオペンチレンサクシネートなどのポリアルキレンサクシネート、ポリエチレンアジペート、ポリブチレンアジペート、ポリネオペンチレンアジペートなどのポリアルキレンアジペート、ポリグリコール酸、ポリ乳酸、ポリリンゴ酸などのポリオキシカルボン酸、ポリプロピオラクトン、ポリカプロラクトンなどのポリラクトンブロック鎖などが挙げられる。 Of these aliphatic polyester block chains, a polyester obtained from a monomer having a C 2-6 alkylene unit can be preferably used. Specific examples include polyalkylene succinates such as polyethylene succinate, polybutylene succinate, polyneopentylene succinate, polyethylene adipate, polybutylene adipate, polyalkylene adipate such as polyneopentylene adipate, polyglycolic acid, poly Examples thereof include polyoxycarboxylic acids such as lactic acid and polymalic acid, and polylactone block chains such as polypropiolactone and polycaprolactone.
これらの脂肪族ポリエステルブロック鎖は、生分解性であるのが好ましく、特に、生産性などの点から、ポリカプロラクトンなどのポリラクトンブロック鎖が好ましい。 These aliphatic polyester block chains are preferably biodegradable, and polylactone block chains such as polycaprolactone are particularly preferable from the viewpoint of productivity.
脂肪族ポリエステルブロック鎖の重量平均分子量（Ｍｗ）は、特に限定されないが、１０００〜５０×１０４、好ましくは３０００〜１０×１０４、さらに好ましくは５０００〜５×１０４（特に８０００〜３×１０４）程度である。ポリラクトンブロック鎖の場合、ラクトンの繰り返し数は、例えば、５〜１０００、好ましくは１０〜５００、さらに好ましくは３０〜３００（特に５０〜２００）程度である。 The weight average molecular weight (Mw) of the aliphatic polyester block chain is not particularly limited, but is 1000 to 50 × 10 4 , preferably 3000 to 10 × 10 4 , more preferably 5000 to 5 × 10 4 (particularly 8000 to 3 ×). About 10 4 ). In the case of a polylactone block chain, the number of lactone repeats is, for example, about 5 to 1000, preferably about 10 to 500, and more preferably about 30 to 300 (particularly about 50 to 200).
脂肪族ポリエステルブロック鎖の分子量分布は、例えば、重量平均分子量（Ｍｗ)／数平均分子量（Ｍｎ）＝１〜５、好ましくは１．１〜３、さらに好ましくは１．２〜２（特に１．３〜１．８）程度である。 The molecular weight distribution of the aliphatic polyester block chain is, for example, weight average molecular weight (Mw) / number average molecular weight (Mn) = 1 to 5, preferably 1.1 to 3, more preferably 1.2 to 2 (particularly 1. 3 to 1.8).
エポキシ基と脂肪族ポリエステルブロック鎖との割合（モル比）は、前者／後者＝５／１〜１００００／１、好ましくは１０／１〜５０００／１、さらに好ましくは２０／１〜３０００／１（特に３０／１〜２０００／１）程度である。 The ratio (molar ratio) between the epoxy group and the aliphatic polyester block chain is the former / the latter = 5/1 to 10000/1, preferably 10/1 to 5000/1, more preferably 20/1 to 3000/1 ( Particularly, it is about 30/1 to 2000/1).
脂肪族ポリエステルブロック鎖の数（グラフト数）は、ビニル系重合体の分子量にもよるが、例えば、平均２〜５００個、好ましくは３〜３００個、さらに好ましくは５〜２００個（特に１０〜１００個）程度である。 The number of aliphatic polyester block chains (number of grafts) depends on the molecular weight of the vinyl polymer, but is, for example, 2 to 500 on average, preferably 3 to 300, more preferably 5 to 200 (particularly 10 to 10). 100).
本発明のビニル系重合体の重量平均分子量は、例えば、１００００〜５００×１０４、好ましくは３００００〜４００×１０４、さらに好ましくは５００００〜３００×１０４（特に１０×１０４〜３００×１０４）程度である。 The vinyl polymer of the present invention has a weight average molecular weight of, for example, 10000 to 500 × 10 4 , preferably 30000 to 400 × 10 4 , more preferably 50000 to 300 × 10 4 (particularly 10 × 10 4 to 300 × 10 4). 4 ) About.
ビニル系重合体の分子量分布は、例えば、Ｍｗ／Ｍｎ＝１〜２０、好ましくは１．１〜１５、さらに好ましくは１．２〜１０（特に１．３〜５）程度である。 The molecular weight distribution of the vinyl polymer is, for example, Mw / Mn = 1 to 20, preferably 1.1 to 15, and more preferably 1.2 to 10 (particularly 1.3 to 5).
［ビニル系重合体の製造方法］
本発明のビニル系重合体は、アクリル系重合体にエポキシ基及び脂肪族ポリエステルブロック鎖を導入できれば特に限定されないが、例えば、グリシジル（メタ）アクリレートと、脂肪族ポリエステルブロック鎖を有するアクリル系マクロモノマーとをラジカル重合させることにより得ることができる。このようなラジカル共重合反応は、慣用の方法、例えば、溶媒の存在下又は非存在下、ラジカル重合開始剤を用いた方法で行うことができる。
[Method for producing vinyl polymer]
The vinyl polymer of the present invention is not particularly limited as long as an epoxy group and an aliphatic polyester block chain can be introduced into the acrylic polymer. For example, an acrylic macromonomer having a glycidyl (meth) acrylate and an aliphatic polyester block chain Can be obtained by radical polymerization. Such radical copolymerization reaction can be performed by a conventional method, for example, a method using a radical polymerization initiator in the presence or absence of a solvent.
溶媒としては、例えば、ケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなど）、エーテル類（ジオキサン、テトラヒドロフランなど）、脂肪族炭化水素類（ヘキサンなど）、脂環式炭化水素類（シクロヘキサンなど）、芳香族炭化水素類（ベンゼン、トルエン、キシレンなど）、ハロゲン化炭素類（ジクロロメタン、ジクロロエタンなど）、エステル類（酢酸メチル、酢酸エチル、酢酸ブチルなど）、水、アルコール類（エタノール、イソプロパノール、ブタノール、シクロヘキサノールなど）、セロソルブ類（メチルセロソルブ、エチルセロソルブなど）、セロソルブアセテート類、スルホキシド類（ジメチルスルホキシドなど）、アミド類（ジメチルホルムアミド、ジメチルアセトアミドなど）などが例示できる。これらの溶媒は、単独で又は二種以上組み合わせて使用できる。これらの溶媒のうち、ベンゼンなどの芳香族炭化水素や、ジメチルホルムアミドなどのアミド類などが汎用される。 Examples of the solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), and alicyclic hydrocarbons (cyclohexane, etc.). , Aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol) , Cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.) Etc. can be exemplified. These solvents can be used alone or in combination of two or more. Of these solvents, aromatic hydrocarbons such as benzene and amides such as dimethylformamide are widely used.
ラジカル重合開始剤としては、例えば、アゾ系化合物（アゾビスイソブチロニトリル（ＡＩＢＮ）、ジメチルアゾイソブチレート、ベンゼンジアゾニウムクロライドなど）、過酸化物（過酸化ベンゾイル、ジ−ｔ−ブチルパーオキシド、ｔ−ブチルパーベンゾエート、過酸化水素等）などが挙げられる。これらのラジカル重合開始剤は、単独で又は二種以上組み合わせて使用できる。これらのラジカル重合開始剤のうち、ＡＩＢＮなどのアゾ系化合物などが汎用される。 Examples of radical polymerization initiators include azo compounds (azobisisobutyronitrile (AIBN), dimethylazoisobutyrate, benzenediazonium chloride, etc.), peroxides (benzoyl peroxide, di-t-butyl peroxide). , T-butyl perbenzoate, hydrogen peroxide, etc.). These radical polymerization initiators can be used alone or in combination of two or more. Of these radical polymerization initiators, azo compounds such as AIBN are widely used.
ラジカル反応は加熱下で行ってもよく、例えば、３０〜１２０℃、好ましくは４０〜１００℃、さらに好ましくは５０〜９０℃（特に５５〜８０℃）程度の温度で行ってもよい。 The radical reaction may be performed under heating. For example, the reaction may be performed at a temperature of about 30 to 120 ° C, preferably 40 to 100 ° C, and more preferably about 50 to 90 ° C (particularly 55 to 80 ° C).
グリシジル（メタ）アクリレートと、アクリル系マクロモノマーとの割合（モル比）は、前記ビニル系重合体の項におけるエポキシ基と脂肪族ポリエステルブロック鎖との割合と同様であり、例えば、５／１〜１００００／１、好ましくは１０／１〜５０００／１、さらに好ましくは２０／１〜３０００／１（特に３０／１〜２０００／１）程度である。本発明では、このような割合で、両者を用いることにより、脂肪族ポリエステルブロック鎖の間隔が適度な間隔となり、エポキシ基による反応性とブロック鎖による相溶性及び生分解性とのバランスが良くなる。 The ratio (molar ratio) between the glycidyl (meth) acrylate and the acrylic macromonomer is the same as the ratio between the epoxy group and the aliphatic polyester block chain in the section of the vinyl polymer. It is about 10,000 / 1, preferably 10/1 to 5000/1, more preferably about 20/1 to 3000/1 (particularly 30/1 to 2000/1). In the present invention, by using both at such a ratio, the space between the aliphatic polyester block chains becomes an appropriate space, and the balance between the reactivity due to the epoxy group and the compatibility and biodegradability due to the block chain is improved. .
脂肪族ポリエステルブロック鎖を有するアクリル系マクロモノマーも、アクリル系モノマーに脂肪族ポリエステルブロック鎖を導入できればよく特に限定されないが、慣用の方法、例えば、ヒドロキシ基を有するアクリル系モノマーを開始剤として用いて、このアクリル系モノマーのヒドロキシ基に対して、前記ラクトン類を開環重合させる方法により得ることができる。 The acrylic macromonomer having an aliphatic polyester block chain is not particularly limited as long as the aliphatic polyester block chain can be introduced into the acrylic monomer, but a conventional method, for example, using an acrylic monomer having a hydroxy group as an initiator. The lactones can be obtained by a ring-opening polymerization method for the hydroxy group of the acrylic monomer.
ヒドロキシ基を有するアクリル系モノマーとしては、前述の（メタ）アクリル酸ヒドロキシアルキルエステルが利用でき、（メタ）アクリル酸２−ヒドロキシエチルなどの（メタ）アクリル酸ヒドロキシＣ２−６アルキルエステルが好ましい。 As the acrylic monomer having a hydroxy group, the above-mentioned (meth) acrylic acid hydroxyalkyl ester can be used, and (meth) acrylic acid hydroxy C 2-6 alkyl ester such as (meth) acrylic acid 2-hydroxyethyl is preferable.
開環重合反応においては、慣用の触媒、例えば、２−エチルヘキシル酸スズ、ジブチルスズオキサイド、ジブチルスズジラウレート、ｎ−ブチルスズヒドロキシオキサイドなどの有機スズ化合物、テトラエチルチタネート、テトラブチルチタネート、テトラプロピルチタネートなどの有機チタン系化合物などを使用するのが好ましい。これらの触媒は、単独で又は二種以上組み合わせて使用できる。これらの触媒のうち、２−エチルヘキシル酸スズなどの有機スズ化合物が好ましい。 In the ring-opening polymerization reaction, a conventional catalyst, for example, organic tin compounds such as tin 2-ethylhexylate, dibutyltin oxide, dibutyltin dilaurate, n-butyltin hydroxyoxide, organic titanium such as tetraethyl titanate, tetrabutyl titanate, tetrapropyl titanate, etc. It is preferable to use a system compound. These catalysts can be used alone or in combination of two or more. Of these catalysts, organotin compounds such as tin 2-ethylhexylate are preferred.
触媒の使用量は、モノマーの総量１００モルに対して、例えば、０．００１〜１０モル、好ましくは０．０１〜５モル、さらに好ましくは０．０５〜１モル（特に０．１〜０．５モル）程度である。 The amount of the catalyst used is, for example, 0.001 to 10 mol, preferably 0.01 to 5 mol, more preferably 0.05 to 1 mol (particularly 0.1 to 0.3 mol) with respect to 100 mol of the total amount of monomers. 5 moles).
開環重合反応は加熱下で行ってもよく、例えば、７０〜２５０℃、好ましくは８０〜２００℃、さらに好ましくは１００〜１８０℃（特に１２０〜１６０℃）程度の温度で行ってもよい。 The ring-opening polymerization reaction may be performed under heating. For example, the ring-opening polymerization reaction may be performed at a temperature of about 70 to 250 ° C, preferably 80 to 200 ° C, and more preferably about 100 to 180 ° C (particularly 120 to 160 ° C).
開環重合反応は、窒素ガスやヘリウムガスなどの不活性ガス条件下であってもよく、空気などの条件下であってもよいが、窒素ガスなどの不活性ガスの雰囲気中で行うのが好ましい。 The ring-opening polymerization reaction may be performed under an inert gas condition such as nitrogen gas or helium gas, or may be performed under air or the like, but may be performed in an inert gas atmosphere such as nitrogen gas. preferable.
ヒドロキシ基を有するアクリル系モノマーと、ラクトン類との割合（モル比）は、例えば、前者／後者＝１／２〜１／１００、好ましくは１／３〜１／５０、さらに好ましくは１／５〜１／３０（特に１／１０〜１／２０）程度である。 The ratio (molar ratio) between the acrylic monomer having a hydroxy group and the lactone is, for example, the former / the latter = 1/2 to 1/100, preferably 1/3 to 1/50, more preferably 1/5. It is about 1/30 (especially 1/10 to 1/20).
このようにして得られたビニル系重合体は、ランダム共重合体であってもよく、ブロック共重合体であってもよい。このビニル系重合体は、反応性基であるエポキシ基（特にグリシジル基）を有するとともに、脂肪族ポリエステルブロック鎖も有しているため、異種のポリマーの相溶性を向上できるとともに、生分解性も優れている。 The vinyl polymer thus obtained may be a random copolymer or a block copolymer. This vinyl polymer has an epoxy group (particularly a glycidyl group) which is a reactive group and also has an aliphatic polyester block chain, so that compatibility of different polymers can be improved and biodegradability can be achieved. Are better.
［相溶化剤］
本発明の相溶化剤は、前記ビニル系重合体で構成されている。本発明の相溶化剤は、互いに相溶性のある複数のポリマーに適用してもよいが、互いに非相溶な複数のポリマー（異種のポリマー）を相溶化するために用いるのが有効である。本発明の相溶化剤は、ポリマーの相溶化作用に優れ、例えば、ポリマーアロイとしてのプラスチックの物性を低下させることなく、異種のポリマー同士を相溶化することができる。
[Compatibilizer]
The compatibilizing agent of the present invention is composed of the vinyl polymer. The compatibilizing agent of the present invention may be applied to a plurality of mutually compatible polymers, but it is effective to use it for compatibilizing a plurality of incompatible polymers (different types of polymers). The compatibilizing agent of the present invention is excellent in the compatibilizing action of the polymer, and can, for example, compatibilize different polymers without deteriorating the physical properties of the plastic as a polymer alloy.
本発明の相溶化剤が適用されるポリマーとしては、例えば、熱可塑性樹脂、熱可塑性エラストマー、ゴム、熱硬化性樹脂などが挙げられる。 Examples of the polymer to which the compatibilizing agent of the present invention is applied include thermoplastic resins, thermoplastic elastomers, rubbers, thermosetting resins, and the like.
熱可塑性樹脂としては、例えば、オレフィン系樹脂（極低密度ポリエチレン、低密度ポリエチレン、線状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレンなどのポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−α−オレフィン共重合体、ポリブテン、ポリメチルペンテン、架橋ポリオレフィン、非晶質ポリオレフィンなど）、ビニル系樹脂（ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルアセタール、エチレン−ビニルアルコール共重合体など）、ハロゲン含有ビニル系樹脂（ポリ塩化ビニル、塩素化ポリエーテル、塩素化ポリエチレン、エチレン−酢酸ビニル−塩化ビニル共重合体、エチレン−塩化ビニル共重合体、アクリロニトリル−塩素化ポリエチレン−スチレン共重合体（ＡＣＳ樹脂）、ポリ塩化ビニリデンなどの塩素含有樹脂、フッ化樹脂など）、アクリル系樹脂（ポリメタクリル酸メチルなど）、ニトリル系樹脂（ニトリル樹脂、ポリエーテルニトリルなど）、スチレン系樹脂（ポリスチレン、アクリロニトリル−スチレン樹脂（ＳＡＮ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、（メタ）アクリル酸エステル−スチレン共重合体（ＭＳ樹脂）、アクリロニトリル−アクリル酸エステル−スチレン共重合体（ＡＡＳ樹脂）、架橋ポリスチレンなど）、ポリカーボネート系樹脂（ビスフェノールＡ型ポリカーボネートなど）、ポリエステル系樹脂（ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリシクロヘキサンジメチレンテレフタレート、ポリエチレンナフタレートなどのポリアルキレンアリレート系樹脂、ポリアリレート系樹脂、アリル樹脂、アルキド樹脂、液晶ポリエステル、脂肪族ポリエステル系樹脂など）、ポリアセタール系樹脂（ポリアセタールなど）、ポリアミド系樹脂（ポリアミド６、ポリアミド６６、ポリアミド４６、ポリアミド６Ｔ、ポリアミドＭＸＤなど）、ポリフェニレンエーテル系樹脂（ポリフェニレンエーテル、変性ポリフェニレンエーテルなど）、ポリスルホン系樹脂（ポリスルホン、ポリエーテルスルホン、ポリアリルスルホンなど）、ポリフェニレンスルフィド系樹脂（ポリフェニレンスルフィドなど）、ポリイミド系樹脂（ポリエーテルイミド、ポリアミドイミド、ポリアミノビスマレイミドなど）、ポリケトン系樹脂、ポリエーテルケトン系樹脂（ポリエーテルケトン、ポリエーテルエーテルケトンなど）、イミダゾール系樹脂（ポリベンズイミダゾールなど）、キシレン樹脂、石油樹脂、アイオノマー樹脂などが挙げられる。 Examples of the thermoplastic resin include olefin resins (very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, etc. polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α. -Olefin copolymer, polybutene, polymethylpentene, crosslinked polyolefin, amorphous polyolefin, etc.), vinyl resin (polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, etc.), halogen-containing vinyl Resin (polyvinyl chloride, chlorinated polyether, chlorinated polyethylene, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS tree ), Chlorine-containing resins such as polyvinylidene chloride, fluororesins, etc., acrylic resins (polymethyl methacrylate, etc.), nitrile resins (nitrile resins, polyethernitriles, etc.), styrene resins (polystyrene, acrylonitrile-styrene) Resin (SAN resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic acid ester-styrene copolymer (MS resin), acrylonitrile-acrylic acid ester-styrene copolymer (AAS resin), Cross-linked polystyrene, etc.), polycarbonate resins (such as bisphenol A polycarbonate), polyester resins (polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate, polyester Polyalkylene arylate resins such as tylene naphthalate, polyarylate resins, allyl resins, alkyd resins, liquid crystal polyesters, aliphatic polyester resins, etc.), polyacetal resins (polyacetal, etc.), polyamide resins (polyamide 6, polyamide 66) , Polyamide 46, polyamide 6T, polyamide MXD, etc.), polyphenylene ether resin (polyphenylene ether, modified polyphenylene ether, etc.), polysulfone resin (polysulfone, polyethersulfone, polyallylsulfone, etc.), polyphenylene sulfide resin (polyphenylene sulfide, etc.) ), Polyimide resins (polyetherimide, polyamideimide, polyaminobismaleimide, etc.), polyketone resins, polyetherketone resins Polyether ketone, polyether ether ketone), imidazole-based resin (polybenzimidazole, etc.), xylene resins, petroleum resins, and ionomer resins.
熱可塑性エラストマーとしては、例えば、ポリアミド系エラストマー、ポリエステル系エラストマー、ポリウレタン系エラストマー、ポリスチレン系エラストマー、ポリオレフィン系エラストマー、ポリジエン系エラストマー、ポリ塩化ビニル系エラストマー、フッ素系熱可塑性エラストマーなどが挙げられる。 Examples of the thermoplastic elastomer include polyamide elastomers, polyester elastomers, polyurethane elastomers, polystyrene elastomers, polyolefin elastomers, polydiene elastomers, polyvinyl chloride elastomers, and fluorine thermoplastic elastomers.
ゴムとしては、例えば、ポリブタジエン（ＢＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）、天然ゴム（ＮＢＲ）、アクリロニトリル−ブタジエンゴム（ニトリルゴム）、ブチルゴムなどが挙げられる。 Examples of the rubber include polybutadiene (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), natural rubber (NBR), acrylonitrile-butadiene rubber (nitrile rubber), and butyl rubber.
熱硬化性樹脂としては、例えば、フェノール樹脂、アミノ樹脂（尿素樹脂、メラミン樹脂など）、フラン樹脂、不飽和ポリエステル系樹脂、エポキシ樹脂、熱硬化性ポリウレタン系樹脂、シリコーン樹脂、熱硬化性ポリイミド系樹脂（ビスマレイミドトリアジン樹脂など）、ジアリルフタレート樹脂、ビニルエステル樹脂（エポキシ樹脂と（メタ）アクリル酸又はその誘導体との反応により得られる樹脂、多価フェノール類とグリシジル（メタ）アクリレートとの反応により得られる樹脂など）、繊維強化プラスチック（ＦＲＰ）などが挙げられる。また、熱硬化性樹脂（又は光硬化性樹脂）には、多官能性（メタ）アクリレート［前記９，９−ビス（ヒドロキシフェニル）フルオレン類の（メタ）アクリレート、（ポリ）ウレタン（メタ）アクリレート、（ポリ）エステル（メタ）アクリレート、エポキシ（メタ）アクリレートなど］、ビニルエーテル（ジオール成分とアセチレンとの反応により得られるジビニルエーテルなど）なども含まれる。 Examples of the thermosetting resin include phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin, unsaturated polyester resin, epoxy resin, thermosetting polyurethane resin, silicone resin, thermosetting polyimide system. Resin (such as bismaleimide triazine resin), diallyl phthalate resin, vinyl ester resin (resin obtained by reaction of epoxy resin and (meth) acrylic acid or its derivatives, reaction of polyhydric phenols with glycidyl (meth) acrylate) Resin obtained), fiber reinforced plastic (FRP), and the like. In addition, the thermosetting resin (or photocurable resin) includes a polyfunctional (meth) acrylate [(meth) acrylate of the 9,9-bis (hydroxyphenyl) fluorenes, (poly) urethane (meth) acrylate]. , (Poly) ester (meth) acrylate, epoxy (meth) acrylate, etc.], vinyl ether (divinyl ether obtained by reaction of diol component and acetylene, etc.) and the like.
これらの樹脂のうち、互いに非相溶なポリマーの組み合わせとしては、例えば、脂肪族ポリマーと芳香族ポリマーとの組み合わせ、極性ポリマーと非極性ポリマーとの組み合わせなど挙げられる。また、これらの樹脂は、３種以上のポリマーの組合せであってもよい。 Among these resins, examples of a combination of incompatible polymers include a combination of an aliphatic polymer and an aromatic polymer, and a combination of a polar polymer and a nonpolar polymer. These resins may be a combination of three or more polymers.
特に、ポリオレフィン系樹脂や脂肪族ポリエステル系樹脂などの脂肪族ポリマーと、芳香族ポリエステル系樹脂、ポリカーボネート系樹脂、スチレン系樹脂などの芳香族ポリマーとの組み合わせに実用的に有効である。さらに、相溶性などの点から、エポキシ基と反応性を有する基（例えば、カルボキシル基、アミノ基、イソシアネート基など）を含む樹脂、例えば、ポリエステル系樹脂、ポリアミド系樹脂、ポリウレタン系樹脂を含む組み合わせも好ましい。 In particular, it is practically effective for a combination of an aliphatic polymer such as a polyolefin resin or an aliphatic polyester resin and an aromatic polymer such as an aromatic polyester resin, a polycarbonate resin, or a styrene resin. Furthermore, from the viewpoint of compatibility, a resin containing a group reactive with an epoxy group (for example, a carboxyl group, an amino group, an isocyanate group, etc.), for example, a combination containing a polyester resin, a polyamide resin, or a polyurethane resin Is also preferable.
さらに、本発明の相溶化剤は、生分解性を有するため、生分解性プラスチックの相溶化剤として用いるのも有効である。生分解性プラスチックには、脂肪族ポリエステル系樹脂、脂肪族ポリアミド系樹脂、セルロース誘導体などが挙げられる。本発明の相溶化剤は、脂肪族ポリエステルブロック鎖を有するため、これらの生分解性プラスチックの中でも、脂肪族ポリエステル系樹脂を含むポリマーアロイに有用である。脂肪族ポリエステル系樹脂としては、前記ビニル系重合体の脂肪族ポリエステルブロック鎖と同様の脂肪族ポリエステル系樹脂が例示でき、特に、ポリ乳酸、ポリカプロラクトン、ポリブチレンサクシネートなどが汎用されている。 Furthermore, since the compatibilizer of the present invention has biodegradability, it is also effective to use it as a compatibilizer for biodegradable plastics. Examples of biodegradable plastics include aliphatic polyester resins, aliphatic polyamide resins, and cellulose derivatives. Since the compatibilizing agent of the present invention has an aliphatic polyester block chain, among these biodegradable plastics, it is useful for a polymer alloy containing an aliphatic polyester resin. Examples of the aliphatic polyester resin include aliphatic polyester resins similar to the aliphatic polyester block chain of the vinyl polymer, and in particular, polylactic acid, polycaprolactone, polybutylene succinate and the like are widely used.
複数のポリマーの割合は、得られるアロイプラスチック材料に必要な物性に応じて選択すればよく、特に限定されない。例えば、２種類のポリマーを組み合わせる場合、第１のポリマー／第２のポリマー＝９９／１〜１／９９、好ましくは９５／５〜５／９５、さらに好ましくは９０／１０〜１０／９０程度である。 The ratio of the plurality of polymers may be selected according to physical properties required for the obtained alloy plastic material, and is not particularly limited. For example, when two kinds of polymers are combined, the first polymer / second polymer = 99/1 to 1/99, preferably 95/5 to 5/95, more preferably about 90/10 to 10/90. is there.
相溶化剤の割合としては、例えば、相溶化される複数のポリマーの合計１００重量部に対して、例えば、０．０１〜３０重量部、好ましくは０．０５〜１０重量部、更に好ましくは０．１〜５重量部（特に０．３〜３重量部）程度である。本発明の相溶化剤は、エポキシ基と脂肪族ポリエステルブロック鎖とを組み合わせているため、相溶化力が高く、少量の割合で複数のポリマーを相溶化できる。 The proportion of the compatibilizer is, for example, 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0 to 100 parts by weight of the total of the plurality of polymers to be compatibilized. About 1 to 5 parts by weight (particularly 0.3 to 3 parts by weight). Since the compatibilizing agent of the present invention combines an epoxy group and an aliphatic polyester block chain, the compatibilizing power is high, and a plurality of polymers can be compatibilized in a small proportion.
［樹脂組成物及び成形品］
本発明の樹脂組成物は、このような複数のポリマーと、前記相溶化剤とで構成されている。さらに、本発明の樹脂組成物は、慣用の添加剤を含んでいてもよい。慣用の添加剤としては、例えば、安定剤（老化防止剤、酸化防止剤、オゾン劣化防止剤、紫外線吸収剤、光安定剤、熱安定剤など）、粘着付与剤、可塑剤、軟化剤、滑剤、充填剤、離型剤、難燃剤、帯電防止剤、変性剤、着色剤、カップリング剤、防腐剤、防カビ剤などが挙げられる。これらの添加剤は、単独で又は二種以上組み合わせて使用できる。
[Resin composition and molded product]
The resin composition of the present invention is composed of such a plurality of polymers and the compatibilizing agent. Furthermore, the resin composition of the present invention may contain a conventional additive. Conventional additives include, for example, stabilizers (anti-aging agents, antioxidants, ozone degradation inhibitors, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), tackifiers, plasticizers, softeners, lubricants. , Fillers, mold release agents, flame retardants, antistatic agents, modifiers, colorants, coupling agents, preservatives, antifungal agents and the like. These additives can be used alone or in combination of two or more.
樹脂組成物の調製方法としては、特に限定されることなく、通常の溶融混練方法などを例示できる。溶融混練においては、例えば、ロールニーダー、バンバリーミキサー、インターミックス、１軸押出機、２軸押出機などの混練機を用いることができる。これらの混練機は、２種以上組み合わせて用いてもよい。また、複数のポリマーを混合する方法としては、例えば、予め混合したマスターチップをそのまま又は希釈して使用する方法や、目的とする成形体を製造するための押出機や成形機に、複数のポリマー及び相溶化剤を投入して混合する方法などが挙げられる。 The method for preparing the resin composition is not particularly limited, and examples thereof include a usual melt-kneading method. In the melt kneading, for example, a kneader such as a roll kneader, a Banbury mixer, an intermix, a single screw extruder, a twin screw extruder, or the like can be used. These kneaders may be used in combination of two or more. In addition, as a method for mixing a plurality of polymers, for example, a method of using a master chip mixed in advance as it is or after dilution, or a plurality of polymers in an extruder or a molding machine for producing a target molded body And a method in which a compatibilizer is added and mixed.
複数のポリマーを充分に相溶化させるためには、混合するポリマーの融点以上の温度で充分に混合するのが好ましい。混合温度は、使用する樹脂の種類に応じて適宜選択できるが、例えば、１８０〜４５０℃、好ましくは１００〜４００℃、さらに好ましくは１５０〜３５０℃程度である。さらに、押出機で混合する場合には、スクリューの回転数は、３ｒｐｍ以上（例えば、３〜１０００ｒｐｍ）、好ましくは５〜５００ｒｐｍ、さらに好ましくは１０〜３００ｒｐｍ程度であってもよい。加圧下で混合してもよく、例えば、１０〜２００ｋｇ／ｃｍ２、好ましくは３０〜１５０ｋｇ／ｃｍ２、さらに好ましくは５０〜１００ｋｇ／ｃｍ２程度の加圧下で混合してもよい。 In order to sufficiently compatibilize a plurality of polymers, it is preferable to sufficiently mix them at a temperature equal to or higher than the melting point of the polymers to be mixed. Although mixing temperature can be suitably selected according to the kind of resin to be used, it is 180-450 degreeC, for example, Preferably it is 100-400 degreeC, More preferably, it is about 150-350 degreeC. Furthermore, when mixing with an extruder, the rotation speed of a screw may be 3 rpm or more (for example, 3-1000 rpm), Preferably it is 5-500 rpm, More preferably, about 10-300 rpm may be sufficient. It may be mixed under pressure, e.g., 10 to 200 / cm 2, preferably 30~150kg / cm 2, more preferably may be mixed under pressure of about 50 to 100 / cm 2.
本発明の樹脂組成物は、ポリマーアロイであるにも拘わらず、相溶性が高く、機械的特性に優れ、各種成形品、例えば、フィルム又はシート状成形品、三次元形状の各種成形品として利用できる。さらに、被覆又はコーティング剤、接着剤などとしても利用できる。また、それぞれの用途に応じて、用いるポリマーの種類や配合量に応じて、前記相溶化剤の種類や量を、装置特性、生産性、要求される品質、物性に応じて適宜選択する必要がある。 Despite being a polymer alloy, the resin composition of the present invention has high compatibility, excellent mechanical properties, and is used as various molded products, for example, film or sheet-shaped molded products, various three-dimensional molded products. it can. Further, it can be used as a coating or coating agent, an adhesive, and the like. In addition, according to each application, it is necessary to appropriately select the type and amount of the compatibilizer depending on the type and amount of the polymer to be used, depending on the device characteristics, productivity, required quality, and physical properties. is there.
本発明の成形体は、前記樹脂組成物を用いて、慣用の方法、例えば、押出成形法、射出成形法、熱成形法（ブロー成形法、真空成形法、圧空成形法、真空圧空成形法、プレス成形法など）、カレンダ加工法、発泡成形法、圧縮成形法などの方法により製造できる。これらの成形法のうち、押出成形法や熱成形法、射出成形法などが汎用される。 The molded body of the present invention is obtained by using a conventional method such as an extrusion molding method, an injection molding method, a thermoforming method (blow molding method, vacuum molding method, pressure molding method, vacuum pressure molding method, For example, a press molding method), a calendering method, a foam molding method, and a compression molding method. Of these molding methods, an extrusion molding method, a thermoforming method, an injection molding method, and the like are widely used.
本発明のビニル系重合体は、異種のポリマーを相溶化でき、相溶化剤として利用できる。特に、脂肪族ポリエステルブロック鎖を有し、生分解性にも優れるとともに、脂肪族ポリエステル系樹脂などの生分解性プラスチックの相溶化剤としても適している。 The vinyl polymer of the present invention can compatibilize different polymers and can be used as a compatibilizing agent. In particular, it has an aliphatic polyester block chain, is excellent in biodegradability, and is also suitable as a compatibilizer for biodegradable plastics such as aliphatic polyester resins.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。用いた試薬、各特性の測定方法、マクロモノマーの製造例を以下に示す。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The reagent used, the measuring method of each characteristic, and the production example of a macromonomer are shown below.
［試薬］
ε−カプロラクトン（ＣＬ）：ナカライテスク（株）製、試薬特級、脱水剤として水素化カルシウムを添加して一晩放置した後、水素化カルシウム存在下で減圧蒸留を行ったもの
メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）：和光純薬（株）製、試薬一級、脱水剤として水素化カルシウムを添加して一晩放置した後、モレキュラーシーブ３Ａ存在下で減圧蒸留を行ったもの
２−エチルヘキサン酸すず（II）（エステル化触媒Ｓｎ(Oct)２）：和光純薬（株）製
メタクリル酸グリシジル（ＧＭＡ）：Ａｌｄｒｉｃｈ社製、試薬一級、脱水剤として水素化カルシウムを添加して一晩放置した後、モレキュラーシーブ３Ａ存在下で減圧蒸留を行ったもの
２，２´−アゾビスイソブチロニトリル（ＡＩＢＮ）：和光純薬（株）製、試薬特級、メタノールを用いて再沈殿させて精製したもの
ベンゼン：和光純薬（株）製、試薬特級、脱水剤として水素化カルシウムを添加して一晩放置した後、水素化カルシウム存在下で減圧蒸留を行ったもの
ジメチルホルムアミド（ＤＭＦ）：和光純薬（株）製、有機合成用（脱水）
ジクロロメタン：和光純薬（株）製、試薬特級
メタノール：和光純薬（株）製、試薬特級
ジエチルエーテル：和光純薬（株）製、試薬特級
クロロホルム：和光純薬（株）製、試薬特級
ポリエチレンテレフタレート（ＰＥＴ）：８０℃で１日乾燥したもの。
[reagent]
[epsilon] -caprolactone (CL): manufactured by Nacalai Tesque Co., Ltd., reagent grade, calcium hydride added as a dehydrating agent, left standing overnight, and then distilled under reduced pressure in the presence of calcium hydride 2-hydroxy methacrylate Ethyl (HEMA): Wako Pure Chemical Industries, Ltd., grade 1 reagent, calcium hydride added as a dehydrating agent and allowed to stand overnight, followed by vacuum distillation in the presence of molecular sieve 3A 2-ethylhexanoic acid tin (II) (Esterification catalyst Sn (Oct) 2 ): Wako Pure Chemical Industries, Ltd. Glycidyl methacrylate (GMA): Aldrich, reagent first grade, after adding calcium hydride as a dehydrating agent and allowing to stand overnight , Which was distilled under reduced pressure in the presence of molecular sieve 3A 2,2′-azobisisobutyronitrile (AIBN): manufactured by Wako Pure Chemical Industries, Ltd., reagent grade, meta Benzene: Wako Pure Chemical Industries, Ltd., reagent grade, added calcium hydride as a dehydrating agent and left overnight, then distilled under reduced pressure in the presence of calcium hydride Dimethylformamide (DMF): Wako Pure Chemical Industries, Ltd., for organic synthesis (dehydration)
Dichloromethane: Wako Pure Chemical Industries, reagent grade Methanol: Wako Pure Chemical Co., reagent special grade Diethyl ether: Wako Pure Chemical Co., reagent special grade Chloroform: Wako Pure Chemical Co., reagent grade polyethylene Terephthalate (PET): dried at 80 ° C. for 1 day.
［各特性の評価方法］
（分子量）
ゲル透過クロマトグラフィー（ＧＰＣ）の場合は、３本のポリスチレンゲルカラム（Ｋ−８０６）を備えたクロマトグラフィー装置（（株）島津製作所製、ＳＨＩＭＡＤＺＵ ＬＣ１０）により測定した。溶離液としてはクロロホルム（ＣＨＣｌ３）を用いて、Ｍｎ、Ｍｗ、Ｍｗ／Ｍｎをポリスチレンを標準物質として換算した。
[Evaluation method of each characteristic]
(Molecular weight)
In the case of gel permeation chromatography (GPC), the measurement was performed by a chromatography apparatus (SHIMADZU LC10, manufactured by Shimadzu Corporation) equipped with three polystyrene gel columns (K-806). Using chloroform (CHCl 3 ) as the eluent, Mn, Mw, and Mw / Mn were converted using polystyrene as a standard substance.
核磁気共鳴（１Ｈ−ＮＭＲ）の場合は、核磁気共鳴装置（ＪＥＯＬ ＬＡ−４００、４００ＭＨｚ）を用いて、ＣＤＣｌ３中、２０℃で測定した。 In the case of nuclear magnetic resonance ( 1 H-NMR), measurement was performed at 20 ° C. in CDCl 3 using a nuclear magnetic resonance apparatus (JEOL LA-400, 400 MHz).
（ＧＭＡモノマー数／グラフト数）
１Ｈ−ＮＭＲスペクトルにおけるピーク面積比（脂肪族ポリエステルブロック鎖のメチレン基のピーク及びエポキシ基のメチン基のピーク）、マクロモノマーの分子量、グラフト共重合体の分子量を測定した後、これらの数値に基づいて、ＧＭＡモノマー数／グラフト数（エポキシ基／脂肪族ポリエステルブロック鎖（モル比））を算出した。
(GMA monomer number / graft number)
After measuring the peak area ratio in the 1 H-NMR spectrum (the methylene group peak of the aliphatic polyester block chain and the methine group peak of the epoxy group), the molecular weight of the macromonomer, and the molecular weight of the graft copolymer, Based on this, the number of GMA monomers / the number of grafts (epoxy group / aliphatic polyester block chain (molar ratio)) was calculated.
（顕微鏡観察）
得られたフィルム（ＰＥＴと直鎖状低密度ポリエチレンと相溶化剤とで構成されたフィルム）について、ヘキサフルオロプロパノールと塩化メチレンとの混合溶媒（前者／後者＝７０／３０（容積比））でＰＥＴを抽出した後、走査型電子顕微鏡（ＳＥＭ）（日立製作所（株）製、走査熱量顕微鏡Ｓ−３２００Ｎ）を用いて、加速電圧２０ｋＶで観察した。
(Microscopic observation)
About the obtained film (film comprised with PET, linear low density polyethylene, and a compatibilizer), it is a mixed solvent of hexafluoropropanol and methylene chloride (the former / the latter = 70/30 (volume ratio)). After extracting PET, it was observed at an acceleration voltage of 20 kV using a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd., scanning calorimetric microscope S-3200N).
（引張試験）
得られたフィルムについて、引張試験機（ＫＴＯＴＥＣＨ Ｉｎｃ．社製、ＫＥＳ Ｇ−１）を用いて、室温下、初期チャック間距離１０ｍｍで前記フィルムを取り付け、引張速度０．５ｍｍ／秒で試験を行い、ひずみと応力との関係を測定した。
(Tensile test)
Using the tensile tester (KESTECH Inc., KES G-1), the film was attached at an initial chuck distance of 10 mm and tested at a tensile speed of 0.5 mm / sec. The relationship between strain and stress was measured.
［マクロモノマーの製造例］
製造例１
表１に示す割合で、ベーキングしたガラス容器に、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）及びε−カプロラクトン（ＣＬ）を仕込み、窒素気流下、エステル化触媒を添加しながら、３０℃で２時間攪拌したが反応は進まなかった。
[Example of production of macromonomer]
Production Example 1
In a ratio shown in Table 1, 2-hydroxyethyl methacrylate (HEMA) and ε-caprolactone (CL) were charged into a baked glass container and stirred at 30 ° C. for 2 hours while adding an esterification catalyst under a nitrogen stream. However, the reaction did not proceed.
製造例２
表１に示す割合で、ベーキングしたガラス容器に、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）及びε−カプロラクトン（ＣＬ）を仕込み、窒素気流下、エステル化触媒を添加しながら、６０℃で２時間攪拌したが反応は進まなかった。
Production Example 2
In the ratio shown in Table 1, 2-hydroxyethyl methacrylate (HEMA) and ε-caprolactone (CL) were charged into a baked glass container and stirred at 60 ° C. for 2 hours while adding an esterification catalyst in a nitrogen stream. However, the reaction did not proceed.
製造例３
表１に示す割合で、ベーキングしたガラス容器に、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）及びε−カプロラクトン（ＣＬ）を仕込み、窒素気流下、エステル化触媒を添加しながら、１００℃で２時間攪拌して、ＣＬの開環重合を行った。その後、０℃の氷水で急冷して反応を停止させた。さらに、未反応のＨＥＭＡやＣＬを除去するために、この未精製反応物をジクロロメタンに溶解し、１０倍過剰のメタノール中に滴下し、ポリマーを沈殿させた。その後、ベンゼンを用いて凍結乾燥を行い、表１に示す分子量を有するマクロモノマーａを得た。マクロモノマーａについて、１Ｈ−ＮＭＲスペクトルを測定した結果を図１に示す。
Production Example 3
In a ratio shown in Table 1, 2-hydroxyethyl methacrylate (HEMA) and ε-caprolactone (CL) were charged into a baked glass container, and stirred at 100 ° C. for 2 hours while adding an esterification catalyst under a nitrogen stream. Then, ring-opening polymerization of CL was performed. Thereafter, the reaction was stopped by quenching with 0 ° C. ice water. Further, in order to remove unreacted HEMA and CL, this unpurified reaction product was dissolved in dichloromethane and dropped into 10-fold excess of methanol to precipitate a polymer. Then, freeze-drying was performed using benzene, and macromonomer a having the molecular weight shown in Table 1 was obtained. The result of having measured the < 1 > H-NMR spectrum about the macromonomer a is shown in FIG.
製造例４
表１に示す割合で、ベーキングしたガラス容器に、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）及びε−カプロラクトン（ＣＬ）を仕込み、窒素気流下、１４０℃で３時間攪拌したが反応は進まなかった。
Production Example 4
In a ratio shown in Table 1, 2-hydroxyethyl methacrylate (HEMA) and ε-caprolactone (CL) were charged into a baked glass container and stirred at 140 ° C. for 3 hours in a nitrogen stream, but the reaction did not proceed.
製造例５
表１に示す割合で、ベーキングしたガラス容器に、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）及びε−カプロラクトン（ＣＬ）を仕込み、窒素気流下、エステル化触媒を添加しながら、１４０℃で３時間攪拌して、ＣＬの開環重合を行った。その後、０℃の氷水で急冷して反応を停止させた。さらに、未反応のＨＥＭＡやＣＬを除去するために、この未精製反応物をジクロロメタンに溶解し、１０倍過剰のメタノール中に滴下し、ポリマーを沈殿させた。その後、ベンゼンを用いて凍結乾燥を行い、表１に示す分子量を有するマクロモノマーｂを得た。
Production Example 5
In a ratio shown in Table 1, 2-hydroxyethyl methacrylate (HEMA) and ε-caprolactone (CL) were charged into a baked glass container and stirred at 140 ° C. for 3 hours while adding an esterification catalyst under a nitrogen stream. Then, ring-opening polymerization of CL was performed. Thereafter, the reaction was stopped by quenching with 0 ° C. ice water. Further, in order to remove unreacted HEMA and CL, this unpurified reaction product was dissolved in dichloromethane and dropped into 10-fold excess of methanol to precipitate a polymer. Then, freeze-drying was performed using benzene, and the macromonomer b having the molecular weight shown in Table 1 was obtained.
製造例６及び７
反応時間を、それぞれ１２時間、０．５時間とする以外は製造例５と同様にして、マクロモノマーｃ及びｄを得た。
Production Examples 6 and 7
Macromonomers c and d were obtained in the same manner as in Production Example 5 except that the reaction times were 12 hours and 0.5 hours, respectively.
製造例８
表１に示す割合で、ベーキングしたガラス容器に、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）及びε−カプロラクトン（ＣＬ）を仕込み、窒素気流下、エステル化触媒を添加しながら、１４０℃で２時間攪拌して、ＣＬの開環重合を行った。その後、０℃の氷水で急冷して反応を停止させた。さらに、未反応のＨＥＭＡやＣＬを除去するために、この未精製反応物をジクロロメタンに溶解し、１０倍過剰のメタノール中に滴下し、ポリマーを沈殿させた。その後、ベンゼンを用いて凍結乾燥を行い、表１に示す分子量を有するマクロモノマーｅを得た。
Production Example 8
In a ratio shown in Table 1, 2-hydroxyethyl methacrylate (HEMA) and ε-caprolactone (CL) were charged into a baked glass container and stirred at 140 ° C. for 2 hours while adding an esterification catalyst under a nitrogen stream. Then, ring-opening polymerization of CL was performed. Thereafter, the reaction was stopped by quenching with 0 ° C. ice water. Further, in order to remove unreacted HEMA and CL, this unpurified reaction product was dissolved in dichloromethane and dropped into 10-fold excess of methanol to precipitate a polymer. Then, freeze-drying was performed using benzene, and the macromonomer e having the molecular weight shown in Table 1 was obtained.
製造例９及び１０
反応時間を、それぞれ１時間、０．５時間とする以外は製造例８と同様にして、マクロモノマーｆ及びｇを得た。
Production Examples 9 and 10
Macromonomers f and g were obtained in the same manner as in Production Example 8, except that the reaction time was 1 hour and 0.5 hour, respectively.
製造例１１
触媒量を半分にし、反応時間を０．５時間とする以外は製造例８と同様にして、マクロモノマーｈを得た。
Production Example 11
Macromonomer h was obtained in the same manner as in Production Example 8 except that the catalyst amount was halved and the reaction time was 0.5 hour.
実施例１
ベンゼン３０ｍｌ中で、表２に示す割合で、開始剤としてＡＩＢＮを用い、マクロモノマーｇと、メタクリル酸グリシジル（ＧＭＡ）とを６０℃で７日間ラジカル共重合させた。この重合反応は０℃の氷水で急冷させて停止させた。反応生成物を１０倍過剰のジエチルエーテル中に滴下し、ポリマーを沈殿させた。その後、ベンゼンを用いて凍結乾燥し、グラフト共重合体Ａを得た。得られたグラフト共重合体Ａの分子量（Ｍｗ）及びＧＭＡモノマー数／グラフト数を測定した結果を表２に示す。さらに、グラフト共重合体Ａについて、１Ｈ−ＮＭＲスペクトルを測定した結果を図１に示す。
Example 1
In 30 ml of benzene, AIBN was used as an initiator at a ratio shown in Table 2, and macromonomer g and glycidyl methacrylate (GMA) were radically copolymerized at 60 ° C. for 7 days. The polymerization reaction was stopped by quenching with 0 ° C. ice water. The reaction product was dropped into a 10-fold excess of diethyl ether to precipitate the polymer. Thereafter, the copolymer was freeze-dried using benzene to obtain graft copolymer A. Table 2 shows the results of measuring the molecular weight (Mw) and the number of GMA monomers / number of grafts of the obtained graft copolymer A. Furthermore, the result of having measured the < 1 > H-NMR spectrum about the graft copolymer A is shown in FIG.
実施例２〜８
表２に示す条件で、ラジカル共重合させる以外は実施例１と同様にしてグラフト共重合体Ｂ〜Ｈを得た。結果を表２に示す。
Examples 2-8
Under the conditions shown in Table 2, graft copolymers B to H were obtained in the same manner as in Example 1 except that radical copolymerization was performed. The results are shown in Table 2.
実施例９
ジメチルホルムアミド（ＤＭＦ）３０ｍｌ中で、表２に示す割合で、開始剤としてＡＩＢＮを用い、マクロモノマーｇと、メタクリル酸グリシジル（ＧＭＡ）とを６０℃で４日間ラジカル共重合させた。この重合反応は０℃の氷水で急冷させて停止させた。反応生成物を１０倍過剰のジエチルエーテル中に滴下し、ポリマーを沈殿させた。その後、ベンゼンを用いて凍結乾燥し、グラフト共重合体Ｉを得た。得られたグラフト共重合体Ｉの分子量（Ｍｗ）及びＧＭＡモノマー数／グラフト数を測定した結果を表２に示す。
Example 9
In 30 ml of dimethylformamide (DMF), AIBN was used as an initiator at a ratio shown in Table 2, and macromonomer g and glycidyl methacrylate (GMA) were radically copolymerized at 60 ° C. for 4 days. The polymerization reaction was stopped by quenching with 0 ° C. ice water. The reaction product was dropped into a 10-fold excess of diethyl ether to precipitate the polymer. Thereafter, the copolymer was freeze-dried using benzene to obtain graft copolymer I. Table 2 shows the results of measuring the molecular weight (Mw) and the number of GMA monomers / number of grafts of the obtained graft copolymer I.
実施例１０〜１１
表２に示す条件で、ラジカル共重合させる以外は実施例９と同様にしてグラフト共重合体Ｊ及びＫを得た。結果を表２に示す。
Examples 10-11
Graft copolymers J and K were obtained in the same manner as in Example 9 except that radical copolymerization was performed under the conditions shown in Table 2. The results are shown in Table 2.
実施例１２
ＰＥＴ８０重量部、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）２０重量部、及び実施例１で得られたグラフト共重合体Ａ１重量部を、混練機（東洋精機（株）製、ＬＡＢＯ ＰＬＡＳＴＯＭＩＬＬ ５０Ｍ）を用いて、温度２８０℃、回転数１０ｒｐｍで２分間混練した後、回転数を２０ｒｐｍに上げて更に８分間混練して、ペレットを得た。得られたペレットを、卓上プレス機（（株）神藤金属工業所製）を用いて、温度２８０℃、圧力６５〜７０ｋｇｆ／ｃｍ２の下で、１２０秒間プレスしてフィルムを得た。得られたフィルムのＳＥＭ写真を図３に示す。この写真から、ＬＬＤＰＥ粒子の平均粒径は８〜１０μｍ程度と小さく、ＬＬＤＰＥとＰＥＴとの相溶性が高いことがわかる。
Example 12
80 parts by weight of PET, 20 parts by weight of linear low-density polyethylene (LLDPE), and 1 part by weight of the graft copolymer A obtained in Example 1 were used in a kneader (Toyo Seiki Co., Ltd., LABO PLASTOMILL 50M). Then, after kneading for 2 minutes at a temperature of 280 ° C. and a rotation speed of 10 rpm, the rotation speed was increased to 20 rpm and further kneading for 8 minutes to obtain pellets. The obtained pellets were pressed for 120 seconds under a temperature of 280 ° C. and a pressure of 65 to 70 kgf / cm 2 using a desktop press machine (manufactured by Shindo Metal Industry Co., Ltd.) to obtain a film. An SEM photograph of the obtained film is shown in FIG. From this photograph, it can be seen that the average particle size of the LLDPE particles is as small as about 8 to 10 μm, and the compatibility between LLDPE and PET is high.
実施例１３
グラフト共重合体Ａの代わりに、実施例５で得られたグラフト共重合体Ｅ（１重量部）を用いる以外は実施例１２と同様にしてフィルムを得た。得られたフィルムのＳＥＭ写真を図４に示す。この写真から、ＬＬＤＰＥ粒子の平均粒径は約３μｍと非常に小さく、ＬＬＤＰＥとＰＥＴとの相溶性が極めて高いことがわかる。さらに、このフィルムについては、引張試験を行った結果を図５に示す。図５から明らかなように、このフィルムは、破断点伸度が高く、機械的特性にも優れている。
Example 13
A film was obtained in the same manner as in Example 12 except that instead of the graft copolymer A, the graft copolymer E (1 part by weight) obtained in Example 5 was used. An SEM photograph of the obtained film is shown in FIG. From this photograph, it can be seen that the average particle size of the LLDPE particles is as small as about 3 μm, and the compatibility between LLDPE and PET is extremely high. Furthermore, about this film, the result of having done the tension test is shown in FIG. As is apparent from FIG. 5, this film has a high elongation at break and excellent mechanical properties.
実施例１４
グラフト共重合体Ａの代わりに、実施例７で得られたグラフト共重合体Ｇ（１重量部）を用いる以外は実施例１２と同様にしてフィルムを得た。得られたフィルムのＳＥＭ写真を図６に示す。この写真から、ＬＬＤＰＥ粒子の平均粒径は約６μｍと小さく、ＬＬＤＰＥとＰＥＴとの相溶性が高いことがわかる。さらに、このフィルムについては、引張試験を行った結果を図７に示す。図７から明らかなように、このフィルムは、破断点伸度が高く、機械的特性にも優れている。
Example 14
A film was obtained in the same manner as in Example 12, except that instead of the graft copolymer A, the graft copolymer G (1 part by weight) obtained in Example 7 was used. An SEM photograph of the obtained film is shown in FIG. From this photograph, it can be seen that the average particle size of the LLDPE particles is as small as about 6 μm and the compatibility between LLDPE and PET is high. Furthermore, about this film, the result of having done the tension test is shown in FIG. As is apparent from FIG. 7, this film has a high elongation at break and excellent mechanical properties.
実施例１５
グラフト共重合体Ａの代わりに、実施例１０で得られたグラフト共重合体Ｊ（１重量部）を用いる以外は実施例１２と同様にしてフィルムを得た。得られたフィルムのＳＥＭ写真を図８に示す。この写真から、ＬＬＤＰＥ粒子の平均粒径は約７μｍと小さく、ＬＬＤＰＥとＰＥＴとの相溶性が高いことがわかる。さらに、このフィルムについては、引張試験を行った結果を図９に示す。図９から明らかなように、このフィルムは、破断点伸度が高く、機械的特性にも優れている。
Example 15
A film was obtained in the same manner as in Example 12 except that instead of the graft copolymer A, the graft copolymer J (1 part by weight) obtained in Example 10 was used. An SEM photograph of the obtained film is shown in FIG. From this photograph, it can be seen that the average particle size of the LLDPE particles is as small as about 7 μm, and the compatibility between LLDPE and PET is high. Furthermore, about this film, the result of having done the tension test is shown in FIG. As is apparent from FIG. 9, this film has a high elongation at break and excellent mechanical properties.
実施例１６
グラフト共重合体Ａの代わりに、実施例１１で得られたグラフト共重合体Ｋ（１重量部）を用いる以外は実施例１２と同様にしてフィルムを得た。得られたフィルムのＳＥＭ写真を図１０に示す。この写真から、ＬＬＤＰＥ粒子の平均粒径は約６μｍと小さく、ＬＬＤＰＥとＰＥＴとの相溶性が高いことがわかる。
Example 16
A film was obtained in the same manner as in Example 12 except that the graft copolymer K (1 part by weight) obtained in Example 11 was used instead of the graft copolymer A. An SEM photograph of the obtained film is shown in FIG. From this photograph, it can be seen that the average particle size of the LLDPE particles is as small as about 6 μm, and the compatibility between LLDPE and PET is high.
比較例１
グラフト共重合体Ａを添加しないことを除き、実施例１２と同様にしてフィルムを得た。得られたフィルムのＳＥＭ写真を図１１に示す。この写真から、ＬＬＤＰＥ粒子の平均粒径は１５〜２３μｍであり、実施例のフィルムに比べて、ＬＬＤＰＥとＰＥＴとの相溶性が低いことがわかる。さらに、このフィルムについては、引張試験を行った結果を図１２に示す。図１２から明らかなように、このフィルムは、５％の伸度によって破断し、機械的特性が充分でない。
Comparative Example 1
A film was obtained in the same manner as in Example 12 except that the graft copolymer A was not added. An SEM photograph of the obtained film is shown in FIG. From this photograph, it can be seen that the average particle size of the LLDPE particles is 15 to 23 μm, and the compatibility between LLDPE and PET is lower than that of the film of the example. Furthermore, about this film, the result of having done the tension test is shown in FIG. As is apparent from FIG. 12, the film breaks with an elongation of 5% and the mechanical properties are not sufficient.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006130718A JP5032790B2 (en) | 2006-05-09 | 2006-05-09 | Novel biodegradable compatibilizer and resin composition containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006130718A JP5032790B2 (en) | 2006-05-09 | 2006-05-09 | Novel biodegradable compatibilizer and resin composition containing the same |
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| Publication Number | Publication Date |
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| JP2007302748A true JP2007302748A (en) | 2007-11-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009072677A1 (en) * | 2007-12-07 | 2009-06-11 | Sumitomo Chemical Company, Limited | Method for producing resin composition and molded body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS511533A (en) * | 1974-06-26 | 1976-01-08 | Kansai Paint Co Ltd | NETSUKOKASEIFUNMATSU JOTORYOSOSEIBUTSU |
| JPH0247120A (en) * | 1988-08-10 | 1990-02-16 | Takemoto Oil & Fat Co Ltd | Graft copolymer having reactivity useful as resin additive and preparation thereof |
| JPH0559137A (en) * | 1991-08-30 | 1993-03-09 | Daicel Chem Ind Ltd | New copolymer grafted with polycaprolactone |
| JPH06298921A (en) * | 1993-04-15 | 1994-10-25 | Mitsui Toatsu Chem Inc | Macromonomer and its polymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS511533A (en) * | 1974-06-26 | 1976-01-08 | Kansai Paint Co Ltd | NETSUKOKASEIFUNMATSU JOTORYOSOSEIBUTSU |
| JPH0247120A (en) * | 1988-08-10 | 1990-02-16 | Takemoto Oil & Fat Co Ltd | Graft copolymer having reactivity useful as resin additive and preparation thereof |
| JPH0559137A (en) * | 1991-08-30 | 1993-03-09 | Daicel Chem Ind Ltd | New copolymer grafted with polycaprolactone |
| JPH06298921A (en) * | 1993-04-15 | 1994-10-25 | Mitsui Toatsu Chem Inc | Macromonomer and its polymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009072677A1 (en) * | 2007-12-07 | 2009-06-11 | Sumitomo Chemical Company, Limited | Method for producing resin composition and molded body |
| US9000093B2 (en) | 2007-12-07 | 2015-04-07 | Sumitomo Chemical Company, Limited | Method for producing resin composition and molded article |
| DE112008003300B4 (en) * | 2007-12-07 | 2020-12-24 | Sumitomo Chemical Company, Ltd. | Process for producing a resin composition and molded article |
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