JP2023152997A - Ethylene-vinyl alcohol copolymer composition, multilayer structure, method for producing ethylene-vinyl alcohol copolymer composition, and method for producing multilayer structure - Google Patents
Ethylene-vinyl alcohol copolymer composition, multilayer structure, method for producing ethylene-vinyl alcohol copolymer composition, and method for producing multilayer structure Download PDFInfo
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- JP2023152997A JP2023152997A JP2023054965A JP2023054965A JP2023152997A JP 2023152997 A JP2023152997 A JP 2023152997A JP 2023054965 A JP2023054965 A JP 2023054965A JP 2023054965 A JP2023054965 A JP 2023054965A JP 2023152997 A JP2023152997 A JP 2023152997A
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- ethylene
- evoh resin
- vinyl alcohol
- alcohol copolymer
- resin composition
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- 238000000465 moulding Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 151
- 238000000034 method Methods 0.000 claims description 49
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 17
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- 244000294411 Mirabilis expansa Species 0.000 description 2
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 1
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- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、エチレン-ビニルアルコール系共重合体(以下、「EVOH樹脂」と称することがある)組成物、多層構造体、EVOH樹脂組成物の製造方法、及び多層構造体の製造方法に関する。 The present invention relates to an ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as "EVOH resin") composition, a multilayer structure, a method for producing an EVOH resin composition, and a method for producing a multilayer structure.
EVOH樹脂は、透明性、酸素等のガスバリア性、保香性、耐溶剤性、耐油性、機械強度等に優れており、フィルム、シート、ボトル等に成形され、食品包装材料、医薬品包装材料、工業薬品包装材料、農薬包装材料等の各種包装材料として広く用いられている。そして、このようなシート状やフィルム状の包装材料は、前記EVOH樹脂単独で作製することが可能であるが、通常、耐水性や強度、他の機能を付与するために、接着剤層を介して、ポリオレフィン系樹脂等を積層した多層構造体として用いることが多い。 EVOH resin has excellent transparency, gas barrier properties against oxygen and other gases, aroma retention, solvent resistance, oil resistance, mechanical strength, etc., and can be molded into films, sheets, bottles, etc., and is used as food packaging materials, pharmaceutical packaging materials, It is widely used as a variety of packaging materials such as industrial drug packaging materials and agricultural chemical packaging materials. Although such sheet-like or film-like packaging materials can be made from the EVOH resin alone, they are usually made using an adhesive layer to provide water resistance, strength, and other functions. Therefore, it is often used as a multilayer structure made by laminating polyolefin resins and the like.
また、前記多層構造体から容器等の成形物を製造した後に発生する、成形物の屑、端部等の不要部分や不良品、あるいは成形物を各種用途に使用した後のごみ等のスクラップを回収して溶融成形し、その回収物を多層構造体の少なくとも1層に、リサイクル層(以下「リグラインド層」と称することがある)として再利用することがある。このような回収物を用いる場合、成形物の変色を防ぎ、かつEVOH樹脂の分解物に由来する目やにの発生を抑制し、外観に優れた成形物が求められている。
かかる外観不良等を改善するために、エチレン-酢酸ビニル共重合体のケン化物と熱可塑性樹脂、例えばポリオレフィン系樹脂の組成物に高級脂肪酸金属塩およびハイドロタルサイト等を配合した樹脂組成物が提案されている(特許文献1を参照)。
In addition, scraps such as scraps of molded products, unnecessary parts such as edges, and defective products generated after manufacturing molded products such as containers from the multilayer structure, and garbage after using the molded products for various purposes, can be removed. The material may be collected and melt-molded, and the collected material may be reused as a recycled layer (hereinafter sometimes referred to as a "regrind layer") in at least one layer of a multilayer structure. When using such a recovered product, there is a demand for a molded product that prevents discoloration of the molded product, suppresses the generation of eye discharge resulting from decomposed products of the EVOH resin, and has an excellent appearance.
In order to improve such poor appearance, a resin composition has been proposed in which a saponified product of ethylene-vinyl acetate copolymer and a thermoplastic resin, such as a polyolefin resin, are blended with higher fatty acid metal salts, hydrotalcite, etc. (See Patent Document 1).
前記特許文献1で開示されている樹脂組成物は、外観不良がある程度改善されているものの、溶融混練や溶融成形等の加熱時に熱劣化しやすい傾向があることから、ロングラン性に対する改善が求められている。また、成形物を回収して再利用した場合の成形物における、さらなる品質向上も求められている。 Although the resin composition disclosed in Patent Document 1 has improved appearance defects to some extent, it tends to suffer thermal deterioration during heating during melt-kneading, melt-molding, etc., so improvements in long-run properties are required. ing. There is also a need for further quality improvements in molded products when the molded products are collected and reused.
本発明は、溶融成形等の加熱時のEVOH樹脂の熱劣化が抑制されており、ロングラン性に優れるとともに、再利用にも適したEVOH樹脂組成物の提供を目的とする。 An object of the present invention is to provide an EVOH resin composition in which thermal deterioration of the EVOH resin during heating during melt molding or the like is suppressed, has excellent long-run properties, and is suitable for reuse.
しかるに、本発明者はかかる事情に鑑み、EVOH樹脂にポリオレフィン系樹脂と特定微量のチタン化合物を加えることにより、溶融成形等の加熱時のEVOH樹脂の熱劣化が抑制されたEVOH樹脂組成物が得られることを見出した。 However, in view of such circumstances, the present inventors have obtained an EVOH resin composition in which thermal deterioration of the EVOH resin during heating during melt molding etc. is suppressed by adding a polyolefin resin and a specific trace amount of a titanium compound to the EVOH resin. I found out that it can be done.
すなわち、本発明は、以下の態様を有する。
[1] EVOH樹脂(A)、ポリオレフィン系樹脂(B)、及びチタン化合物(C)を含有するEVOH樹脂組成物であって、
前記チタン化合物(C)の金属換算含有量が、EVOH樹脂組成物の質量あたり0.00005ppm以上0.5ppm未満であるEVOH樹脂組成物。
[2] 前記ポリオレフィン系樹脂(B)に対するEVOH樹脂(A)の質量含有比率(A)/(B)が、1/99~99/1である[1]記載のEVOH樹脂組成物。
[3] 前記EVOH樹脂(A)とチタン化合物(C)の総和質量あたりのチタン化合物(C)の金属換算含有量が、0.001~3ppmである[1]又は[2]記載のEVOH樹脂組成物。
[4] 前記ポリオレフィン系樹脂(B)が、密度が0.89g/cm3以上のポリオレフィン系樹脂である[1]~[3]のいずれかに記載のEVOH樹脂組成物。
[5] 前記ポリオレフィン系樹脂(B)がポリプロピレンである[4]記載のEVOH樹脂組成物。
[6] [1]~[5]のいずれかに記載のEVOH樹脂組成物からなる層を少なくとも1層備える多層構造体。
[7] [1]~[5]のいずれかに記載のEVOH樹脂組成物を製造する方法であって、
前記EVOH樹脂とチタン化合物とを含有する組成物原料を溶融混合する工程を備える、EVOH樹脂組成物の製造方法。
[8] [6]記載の多層構造体を製造する方法であって、
前記EVOH樹脂組成物からなる層を溶融成形する工程を備える、多層構造体の製造方法。
That is, the present invention has the following aspects.
[1] An EVOH resin composition containing an EVOH resin (A), a polyolefin resin (B), and a titanium compound (C),
An EVOH resin composition in which the content of the titanium compound (C) in terms of metal is 0.00005 ppm or more and less than 0.5 ppm per mass of the EVOH resin composition.
[2] The EVOH resin composition according to [1], wherein the mass content ratio (A)/(B) of the EVOH resin (A) to the polyolefin resin (B) is 1/99 to 99/1.
[3] The EVOH resin according to [1] or [2], wherein the content of the titanium compound (C) in terms of metal per total mass of the EVOH resin (A) and the titanium compound (C) is 0.001 to 3 ppm. Composition.
[4] The EVOH resin composition according to any one of [1] to [3], wherein the polyolefin resin (B) is a polyolefin resin having a density of 0.89 g/cm 3 or more.
[5] The EVOH resin composition according to [4], wherein the polyolefin resin (B) is polypropylene.
[6] A multilayer structure comprising at least one layer made of the EVOH resin composition according to any one of [1] to [5].
[7] A method for producing the EVOH resin composition according to any one of [1] to [5], comprising:
A method for producing an EVOH resin composition, comprising a step of melt-mixing composition raw materials containing the EVOH resin and a titanium compound.
[8] A method for manufacturing the multilayer structure according to [6], comprising:
A method for producing a multilayer structure, comprising the step of melt-molding a layer made of the EVOH resin composition.
本発明のEVOH樹脂組成物は、熱安定性に優れるため、溶融混練時や溶融成形時等の加熱時におけるEVOH樹脂の熱劣化を抑制することができる。特に、比較的高密度の、機械的強度に優れたポリオレフィン系樹脂(B)を含むものは、とりわけ高品質の成形物を得ることができ好適である。 Since the EVOH resin composition of the present invention has excellent thermal stability, it is possible to suppress thermal deterioration of the EVOH resin during heating during melt-kneading, melt-molding, and the like. In particular, those containing a polyolefin resin (B) having a relatively high density and excellent mechanical strength are particularly suitable since they can yield particularly high quality molded products.
また、本発明の樹脂組成物からなる層を備える多層構造体は、溶融混練時や溶融成形時等の加熱時におけるEVOH樹脂の熱劣化が抑制されることから、各種成形物、例えば、食品、薬品、農薬等の包装材料として、好適に用いることができる。そして、再利用を前提とする成形物を得る場合や、比較的機械的強度が要求される成形物を得る場合、より高品質な成形物を提供することができ、好適である。 In addition, the multilayer structure including the layer made of the resin composition of the present invention suppresses thermal deterioration of the EVOH resin during heating during melt-kneading and melt-molding, so it can be used for various molded products, such as foods, etc. It can be suitably used as a packaging material for medicines, agricultural chemicals, etc. Further, when obtaining a molded product intended for reuse or a molded product requiring relatively high mechanical strength, it is possible to provide a molded product of higher quality, which is suitable.
以下、本発明の実施形態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形態に限定されない。
なお、本発明において「X~Y」(X,Yは任意の数字)と表現する場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」又は「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)又は「Y以下」(Yは任意の数字)と表現した場合、「Xより大きいことが好ましい」又は「Y未満であることが好ましい」旨の意も包含する。
なお、本発明において、「x及び/又はy(x,yは任意の構成又は成分)」とは、xのみ、yのみ、x及びy、という3通りの組合せを意味するものである。
Hereinafter, the present invention will be described in more detail based on embodiments of the present invention, but the present invention is not limited to these embodiments.
In addition, in the present invention, when expressed as "X to Y" (X, Y are arbitrary numbers), unless otherwise specified, it means "more than or equal to X and less than or equal to Y", and also means "preferably greater than X" or "preferably It also includes the meaning of "less than Y".
In addition, when expressed as "more than or equal to X" (X is any number) or "less than or equal to Y" (Y is any number), it is also possible to indicate that "it is preferably greater than X" or "it is preferably less than Y". It also includes meaning.
In the present invention, "x and/or y (x, y are arbitrary structures or components)" means three combinations: x only, y only, and x and y.
<EVOH樹脂組成物>
本発明の一実施態様に係るEVOH樹脂組成物(以下、「本EVOH樹脂組成物」と称する)は、EVOH樹脂(A)と、特定のポリオレフィン系樹脂(B)と、特定微量のチタン化合物(C)とを含有するものである。
以下、各成分について説明する。
<EVOH resin composition>
The EVOH resin composition according to one embodiment of the present invention (hereinafter referred to as "this EVOH resin composition") comprises an EVOH resin (A), a specific polyolefin resin (B), and a specific trace amount of a titanium compound ( C).
Each component will be explained below.
[EVOH樹脂(A)]
本発明で用いるEVOH樹脂(A)は、通常、エチレンとビニルエステル系モノマーとの共重合体であるエチレン-ビニルエステル系共重合体をケン化させることにより得られる樹脂であり、非水溶性の熱可塑性樹脂である。
[EVOH resin (A)]
The EVOH resin (A) used in the present invention is usually a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble resin. It is a thermoplastic resin.
前記ビニルエステル系モノマーとしては、市場入手性や製造時の不純物処理効率がよい点から、代表的には酢酸ビニルが用いられる。酢酸ビニル以外の他のビニルエステル系モノマーとしては、例えばギ酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、バーサチック酸ビニル等の脂肪族ビニルエステル、安息香酸ビニル等の芳香族ビニルエステル等があげられるが、通常炭素数3~20、好ましくは炭素数4~10、特に好ましくは炭素数4~7の脂肪族ビニルエステルが用いられる。これらは通常単独で用いるが、必要に応じて複数種を同時に用いてもよい。 As the vinyl ester monomer, vinyl acetate is typically used because of its market availability and good efficiency in treating impurities during production. Examples of vinyl ester monomers other than vinyl acetate include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and versatic acid. Examples include aliphatic vinyl esters such as vinyl, aromatic vinyl esters such as vinyl benzoate, and aliphatic vinyls having usually 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. Esters are used. These are usually used alone, but multiple types may be used simultaneously if necessary.
前記エチレンとビニルエステル系モノマーとを共重合させる重合法としては、公知の任意の重合法、例えば溶液重合、懸濁重合、エマルジョン重合等を用いて行うことができるが、一般的にはメタノールを溶媒とする溶液重合が用いられる。また、得られたエチレン-ビニルエステル系共重合体のケン化も公知の方法で行い得る。
このようにして製造されるEVOH樹脂(A)は、エチレン由来の構造単位とビニルアルコール構造単位を主とし、ケン化されずに残存する若干量のビニルエステル構造単位を含むものである。
The copolymerization method for copolymerizing ethylene and the vinyl ester monomer can be carried out using any known polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization, etc., but generally methanol is used. Solution polymerization using a solvent is used. Furthermore, the obtained ethylene-vinyl ester copolymer may be saponified by a known method.
The EVOH resin (A) produced in this way mainly contains structural units derived from ethylene and vinyl alcohol structural units, and contains a small amount of vinyl ester structural units that remain without being saponified.
前記EVOH樹脂(A)におけるエチレン構造単位の含有量は、通常20~60モル%、好ましくは25~50モル%、特に好ましくは25~35モル%である。前記エチレン構造単位の含有量は、ビニルエステル系モノマーとエチレンとを共重合させる際のエチレンの圧力によって制御することができ、かかる含有量が低すぎる場合は、高湿下のガスバリア性、溶融成形性が低下する傾向があり、逆に高すぎる場合は、ガスバリア性が低下する傾向がある。
なお、かかるエチレン構造単位の含有量は、ISO14663に基づいて測定することができる。
The content of ethylene structural units in the EVOH resin (A) is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 35 mol%. The content of the ethylene structural unit can be controlled by the pressure of ethylene when copolymerizing the vinyl ester monomer and ethylene, and if this content is too low, the gas barrier property under high humidity, melt molding On the other hand, if it is too high, gas barrier properties tend to decrease.
Note that the content of such ethylene structural units can be measured based on ISO14663.
前記EVOH樹脂(A)におけるケン化度は、通常90~100モル%、好ましくは95~100モル%、特に好ましくは99~100モル%である。前記ケン化度は、エチレン-ビニルエステル系共重合体をケン化する際のケン化触媒(通常、水酸化ナトリウム等のアルカリ性触媒が用いられる)の量、温度、時間等によって制御でき、かかるケン化度が低すぎる場合にはガスバリア性、熱安定性、耐湿性等が低下する傾向がある。
かかるEVOH樹脂(A)のケン化度は、JIS K6726(但し、EVOH樹脂は水/メタノール溶媒に均一に溶解した溶液として用いる)に基づいて測定することができる。
The saponification degree of the EVOH resin (A) is usually 90 to 100 mol%, preferably 95 to 100 mol%, particularly preferably 99 to 100 mol%. The degree of saponification can be controlled by the amount, temperature, time, etc. of the saponification catalyst (usually an alkaline catalyst such as sodium hydroxide is used) when saponifying the ethylene-vinyl ester copolymer. If the degree of oxidation is too low, gas barrier properties, thermal stability, moisture resistance, etc. tend to deteriorate.
The degree of saponification of the EVOH resin (A) can be measured based on JIS K6726 (however, the EVOH resin is used as a solution uniformly dissolved in a water/methanol solvent).
前記EVOH樹脂(A)におけるメルトフローレート(MFR)(210℃、荷重2160g)は、通常0.5~100g/10分であり、好ましくは1~50g/10分、特に好ましくは3~35g/10分である。かかるMFRが大きすぎる場合には、製膜時の安定性が損なわれる傾向があり、小さすぎる場合には粘度が高くなり過ぎて溶融押出しが困難となる傾向がある。
前記MFRは、EVOH樹脂(A)の重合度の指標となるものであり、エチレンとビニルエステル系モノマーを共重合する際の重合開始剤の量や、溶媒の量によって調整することができる。
The melt flow rate (MFR) (210°C, load 2160 g) of the EVOH resin (A) is usually 0.5 to 100 g/10 minutes, preferably 1 to 50 g/10 minutes, particularly preferably 3 to 35 g/10 minutes. It's 10 minutes. If the MFR is too large, stability during film formation tends to be impaired, and if it is too small, the viscosity tends to become too high, making melt extrusion difficult.
The MFR is an index of the degree of polymerization of the EVOH resin (A), and can be adjusted by adjusting the amount of polymerization initiator and the amount of solvent when copolymerizing ethylene and vinyl ester monomer.
また、前記EVOH樹脂(A)には、本発明の効果を阻害しない範囲で、以下に示すコモノマーに由来する構造単位が、さらに含まれていてもよい(例えばEVOH樹脂(A)の10モル%以下)。
前記コモノマーとしては、例えばプロピレン、1-ブテン、イソブテン等のオレフィン類、3-ブテン-1-オール、3-ブテン-1,2-ジオール、4-ペンテン-1-オール、5-ヘキセン-1,2-ジオール等のヒドロキシ基含有α-オレフィン類やそのエステル化物、アシル化物等の誘導体;2-メチレンプロパン-1,3-ジオール、3-メチレンペンタン-1,5-ジオール等のヒドロキシアルキルビニリデン類;1,3-ジアセトキシ-2-メチレンプロパン、1,3-ジプロピオニルオキシ-2-メチレンプロパン、1,3-ジブチリルオキシ-2-メチレンプロパン等のヒドロキシアルキルビニリデンジアセテート類;アクリル酸、メタクリル酸、クロトン酸、(無水)フタル酸、(無水)マレイン酸、(無水)イタコン酸等の不飽和酸類あるいはその塩あるいはアルキル基の炭素数が1~18のモノ又はジアルキルエステル類;アクリルアミド、アルキル基の炭素数が1~18のN-アルキルアクリルアミド、N,N-ジメチルアクリルアミド、2-アクリルアミドプロパンスルホン酸あるいはその塩、アクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のアクリルアミド類;メタアクリルアミド、アルキル基の炭素数が1~18のN-アルキルメタクリルアミド、N,N-ジメチルメタクリルアミド、2-メタクリルアミドプロパンスルホン酸あるいはその塩、メタクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のメタクリルアミド類;N-ビニルピロリドン、N-ビニルホルムアミド、N-ビニルアセトアミド等のN-ビニルアミド類;アクリルニトリル、メタクリルニトリル等のシアン化ビニル類;アルキル基の炭素数が1~18のアルキルビニルエーテル、ヒドロキシアルキルビニルエーテル、アルコキシアルキルビニルエーテル等のビニルエーテル類;塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、臭化ビニル等のハロゲン化ビニル化合物類;トリメトキシビニルシラン等のビニルシラン類;酢酸アリル、塩化アリル等のハロゲン化アリル化合物類;アリルアルコール、ジメトキシアリルアルコール等のアリルアルコール類;トリメチル-(3-アクリルアミド-3-ジメチルプロピル)-アンモニウムクロリド、アクリルアミド-2-メチルプロパンスルホン酸等のコモノマーがあげられる。これらは単独でもしくは2種以上併せて用いることができる。
Further, the EVOH resin (A) may further contain a structural unit derived from a comonomer shown below within a range that does not impede the effects of the present invention (for example, 10 mol% of the EVOH resin (A)). below).
Examples of the comonomer include olefins such as propylene, 1-butene, and isobutene, 3-buten-1-ol, 3-buten-1,2-diol, 4-penten-1-ol, 5-hexene-1, Hydroxy group-containing α-olefins such as 2-diol, and derivatives thereof such as esters and acylated products; Hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol ; Hydroxyalkyl vinylidene diacetates such as 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyryloxy-2-methylenepropane; Acrylic acid, methacrylic Acid, unsaturated acids such as crotonic acid, phthalic acid (anhydride), maleic acid (anhydride), and itaconic acid (anhydride), or their salts, or mono- or dialkyl esters with an alkyl group having 1 to 18 carbon atoms; acrylamide, alkyl Acrylamides such as N-alkylacrylamide, N,N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salt, acrylamidepropyldimethylamine, its acid salt, or its quaternary salt; meth Acrylamide, N-alkylmethacrylamide whose alkyl group has 1 to 18 carbon atoms, N,N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or its salt, methacrylamidepropyldimethylamine or its acid salt, or its quaternary Methacrylamides such as salts; N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide; vinylcyanides such as acrylonitrile and methacrylnitrile; Vinyl ethers such as alkyl vinyl ether, hydroxyalkyl vinyl ether, and alkoxyalkyl vinyl ether; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and vinyl bromide; Vinyl silanes such as trimethoxyvinylsilane; Allyl acetate , allyl halides such as allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; comonomers such as trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride and acrylamide-2-methylpropanesulfonic acid. can be given. These can be used alone or in combination of two or more.
なかでも、ヒドロキシ基含有α-オレフィン類が好ましく、特には3-ブテン-1,2-ジオール、5-ヘキセン-1,2-ジオールが好ましい。前記ヒドロキシ基含有α-オレフィン類を共重合した場合、得られるEVOH樹脂は、側鎖に1級水酸基を有することとなる。このような側鎖に1級水酸基を有するEVOH樹脂、特には側鎖に1,2-ジオール構造を有するEVOH樹脂は、ガスバリア性を保持しつつ二次成形性が良好になる点で好ましい。 Among these, hydroxy group-containing α-olefins are preferred, with 3-butene-1,2-diol and 5-hexene-1,2-diol being particularly preferred. When the hydroxy group-containing α-olefins are copolymerized, the resulting EVOH resin will have a primary hydroxyl group in the side chain. Such an EVOH resin having a primary hydroxyl group in the side chain, particularly an EVOH resin having a 1,2-diol structure in the side chain, is preferable because it maintains gas barrier properties and has good secondary moldability.
本発明で用いるEVOH樹脂(A)が、側鎖に1級水酸基を有する場合、当該1級水酸基を有するモノマー由来の構造単位の含有量は、EVOH樹脂(A)の通常0.1~20モル%、好ましくは0.5~15モル%、特に好ましくは1~10モル%である。 When the EVOH resin (A) used in the present invention has a primary hydroxyl group in the side chain, the content of the structural unit derived from the monomer having the primary hydroxyl group is usually 0.1 to 20 mol of the EVOH resin (A). %, preferably 0.5 to 15 mol %, particularly preferably 1 to 10 mol %.
また、前記EVOH樹脂(A)としては、エステル化、ウレタン化、アセタール化、シアノエチル化、オキシアルキレン化等の「後変性」されたEVOH樹脂を用いることもできる。 Further, as the EVOH resin (A), it is also possible to use an EVOH resin that has been "post-modified" such as esterification, urethanization, acetalization, cyanoethylation, or oxyalkylenation.
前記後変性されたEVOH樹脂を用いる場合、その変性率は、通常10モル%以下であり、好ましくは4モル%以下である。用いるEVOH樹脂の変性率が高すぎる場合、熱劣化しやすくなり、ロングラン性が低下する傾向がある。 When using the post-modified EVOH resin, the modification rate is usually 10 mol% or less, preferably 4 mol% or less. If the modification rate of the EVOH resin used is too high, it tends to be easily thermally degraded and its long run properties tend to decrease.
さらに、前記EVOH樹脂(A)は、エチレン構造単位の含有量、ケン化度、重合度、共重合成分等が異なるEVOH樹脂の混合物であってもよい。 Further, the EVOH resin (A) may be a mixture of EVOH resins having different contents of ethylene structural units, degrees of saponification, degrees of polymerization, copolymerization components, and the like.
[ポリオレフィン系樹脂(B)]
本発明に用いられるポリオレフィン系樹脂(B)は、特に限定するものではなく、例えば、直鎖状低密度ポリエチレン(LLDPE)、低密度ポリエチレン(LDPE)、超低密度ポリエチレン(VLDPE)、中密度ポリエチレン(MDPE)、高密度ポリエチレン(HDPE)、アイオノマー、エチレン-プロピレン(ブロック又はランダム)共重合体、エチレン-アクリル酸共重合体、エチレン-メタクリル酸共重合体、ポリプロピレン(PP)、プロピレン-α-オレフィン(炭素数4~20のα-オレフィン)共重合体、ポリブテン、ポリペンテン、ポリメチルペンテン等のオレフィンの単独又は共重合体、あるいはこれらのオレフィンの単独又は共重合体を不飽和カルボン酸又はそのエステルでグラフト変性したもの等、広義のポリオレフィン系樹脂をあげることができる。これらは、単独でもしくは2種以上併せて用いることができ、なかでも、機械的強度に優れた成形物を得る上で、ポリプロピレン(PP)やポリエチレン(MDPE、HDPE)およびこれらのブレンド物が好ましい。とりわけ、ポリプロピレンが、効果の点で最適である。
[Polyolefin resin (B)]
The polyolefin resin (B) used in the present invention is not particularly limited, and examples thereof include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), and medium density polyethylene. (MDPE), high density polyethylene (HDPE), ionomer, ethylene-propylene (block or random) copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, polypropylene (PP), propylene-α- Copolymers of olefins (α-olefins having 4 to 20 carbon atoms), monopolymers or copolymers of olefins such as polybutene, polypentene, polymethylpentene, or monopolymers or copolymers of these olefins with unsaturated carboxylic acids or their Examples include polyolefin resins in a broad sense, such as those graft-modified with esters. These can be used alone or in combination of two or more, and among them, polypropylene (PP), polyethylene (MDPE, HDPE), and blends thereof are preferred in order to obtain molded products with excellent mechanical strength. . In particular, polypropylene is optimal in terms of effectiveness.
本発明で用いるポリオレフィン系樹脂(B)は、密度が、通常0.89g/cm3以上であり、好ましくは0.90g/cm3以上0.98g/cm3未満である。例えば、本EVOH樹脂組成物を用いて得られる成形物を再利用する際、EVOH樹脂組成物の機械的強度を補強するために用いられることがあり、そのような用途を企図した場合、より高密度で機械的強度に優れた樹脂組成物とするために、比較的高密度のポリオレフィン系樹脂(B)を用いることが好ましい。 The density of the polyolefin resin (B) used in the present invention is usually 0.89 g/cm 3 or more, preferably 0.90 g/cm 3 or more and less than 0.98 g/cm 3 . For example, when reusing a molded article obtained using the present EVOH resin composition, it may be used to reinforce the mechanical strength of the EVOH resin composition. In order to obtain a resin composition with excellent density and mechanical strength, it is preferable to use a relatively high-density polyolefin resin (B).
本EVOH樹脂組成物において、ポリオレフィン系樹脂(B)に対するEVOH樹脂(A)の質量含有比率(A)/(B)は、好ましくは1/99~99/1であり、より好ましくは2/98~75/25であり、さらに好ましくは3/97~50/50、特に好ましくは4/96~25/75、とりわけ好ましくは5/95~10/90である。EVOH樹脂(A)とオレフィン系ポリマー(B)との質量含有比率が前記の範囲内であると、より熱劣化抑制効果に優れるものとなる。 In the present EVOH resin composition, the mass content ratio (A)/(B) of EVOH resin (A) to polyolefin resin (B) is preferably 1/99 to 99/1, more preferably 2/98. ~75/25, more preferably 3/97 ~ 50/50, particularly preferably 4/96 ~ 25/75, particularly preferably 5/95 ~ 10/90. When the mass content ratio of the EVOH resin (A) and the olefin polymer (B) is within the above range, the effect of suppressing thermal deterioration will be more excellent.
また、本EVOH樹脂組成物におけるEVOH樹脂(A)とポリオレフィン系樹脂(B)の含有量の総和は、通常70質量%以上であり、好ましくは80質量%以上であり、より好ましくは90質量%以上である。なお、EVOH樹脂(A)とポリオレフィン系樹脂(B)の含有量の総和の上限は、樹脂組成物からチタン化合物(C)を除いた全質量である。 Further, the total content of EVOH resin (A) and polyolefin resin (B) in the present EVOH resin composition is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass. That's all. Note that the upper limit of the total content of the EVOH resin (A) and the polyolefin resin (B) is the total mass of the resin composition excluding the titanium compound (C).
[チタン化合物(C)]
本発明に用いられる、前記チタン化合物(C)としては、例えば無機チタン化合物、有機チタン化合物があげられる。なお、チタン化合物は単独でもしくは2種以上を併せて用いてもよい。なかでも無機チタン化合物が好ましい。
[Titanium compound (C)]
Examples of the titanium compound (C) used in the present invention include inorganic titanium compounds and organic titanium compounds. Note that the titanium compounds may be used alone or in combination of two or more. Among them, inorganic titanium compounds are preferred.
前記無機チタン化合物としては、例えばチタン酸化物、チタン水酸化物、チタン塩化物、チタンの無機塩等があげられる。
前記チタン酸化物としては、例えば酸化チタン(II)、酸化チタン(III)、酸化チタン(IV)、亜酸化チタン等があげられる。
前記チタン水酸化物としては、例えば水酸化第一チタン、水酸化第二チタン等があげられる。
前記チタン塩化物としては、例えば塩化第一チタン、塩化第二チタン等があげられる。
前記チタンの無機塩としては、例えばリン酸チタン、硫酸チタン等があげられる。
なかでも、チタン酸化物が好ましく、酸化チタン(IV)がより好ましく、ルチル型の酸化チタン(IV)が特に好ましい。
Examples of the inorganic titanium compound include titanium oxide, titanium hydroxide, titanium chloride, and inorganic salts of titanium.
Examples of the titanium oxide include titanium (II) oxide, titanium (III) oxide, titanium (IV) oxide, and titanium suboxide.
Examples of the titanium hydroxide include titanous titanium hydroxide, titanium dihydroxide, and the like.
Examples of the titanium chloride include titanous titanium chloride and titanium chloride.
Examples of the inorganic salt of titanium include titanium phosphate and titanium sulfate.
Among these, titanium oxide is preferred, titanium (IV) oxide is more preferred, and rutile type titanium (IV) oxide is particularly preferred.
前記有機チタン化合物としては、例えば酢酸チタン、酪酸チタン、ステアリン酸チタン等のカルボン酸チタン等があげられる。 Examples of the organic titanium compound include titanium carboxylates such as titanium acetate, titanium butyrate, and titanium stearate.
なお、前記チタン化合物(C)は、EVOH樹脂組成物中で、チタン化合物として存在する場合の他、イオン化した状態、あるいはEVOH樹脂や他の配位子と相互作用した錯体の状態で存在していてもよい。 In addition, the titanium compound (C) may exist in the EVOH resin composition not only as a titanium compound but also in an ionized state or in a complex state that interacts with the EVOH resin or other ligands. It's okay.
前記チタン化合物(C)の平均粒径は、通常0.001~100μmであり、好ましくは0.01~50μmであり、より好ましくは0.015~20μmである。チタン化合物の平均粒径が前記範囲内であると、熱安定性がより向上する傾向がある。 The average particle size of the titanium compound (C) is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.015 to 20 μm. When the average particle size of the titanium compound is within the above range, thermal stability tends to be further improved.
前記チタン化合物(C)の金属換算含有量は、EVOH樹脂組成物の質量あたり0.00005ppm以上0.5ppm未満である。好ましくは0.0005~0.3ppmであり、より好ましくは0.0015~0.2ppmであり、特に好ましくは0.005~0.1ppmである。チタン化合物(C)の含有量を前記範囲とすることで、溶融成形時の熱劣化を抑制することができ、ロングラン性に優れたものとなる。また、チタン化合物(C)の含有量が少なすぎると、熱劣化を抑制する効果が低下し、含有量が多すぎるとEVOH樹脂(A)の熱分解が起こりやすくなり着色しやすくなる。 The content of the titanium compound (C) in terms of metal is 0.00005 ppm or more and less than 0.5 ppm per mass of the EVOH resin composition. Preferably it is 0.0005 to 0.3 ppm, more preferably 0.0015 to 0.2 ppm, particularly preferably 0.005 to 0.1 ppm. By setting the content of the titanium compound (C) within the above range, thermal deterioration during melt molding can be suppressed, resulting in excellent long-run properties. Moreover, if the content of the titanium compound (C) is too small, the effect of suppressing thermal deterioration will be reduced, and if the content is too large, thermal decomposition of the EVOH resin (A) will easily occur and coloration will occur.
前記チタン化合物(C)の金属換算含有量は、本EVOH樹脂組成物を白金るつぼに計り入れ、バーナー及び電気炉で順次灰化し、かかる灰化物を硝酸及びふっ化水素酸で加熱分解し、希硝酸と希ふっ化水素酸の混酸で処理して定容して得られた定容液中のチタンをICP質量分析装置(Agilent Technologies社製、Agilent 8800)を用い、ICP質量分析法で測定することにより定量することができる。 The metal equivalent content of the titanium compound (C) is determined by weighing the present EVOH resin composition into a platinum crucible, sequentially incinerating it with a burner and an electric furnace, and heating and decomposing the ashed product with nitric acid and hydrofluoric acid. Titanium in a fixed volume solution obtained by treatment with a mixed acid of nitric acid and dilute hydrofluoric acid is measured by ICP mass spectrometry using an ICP mass spectrometer (manufactured by Agilent Technologies, Agilent 8800). It can be quantified by
また、前記EVOH樹脂(A)とチタン化合物(C)の総和質量あたりのチタン化合物(C)の金属換算含有量は、好ましくは0.001~3ppmであり、より好ましくは0.03~1ppmであり、特に好ましくは0.05~0.5ppmである。
チタン化合物(C)の含有量が少なすぎると、熱劣化を抑制する効果が低下し、含有量が多すぎるとEVOH樹脂(A)の熱分解が起こりやすくなり着色しやすくなる。
Further, the metal equivalent content of the titanium compound (C) per the total mass of the EVOH resin (A) and the titanium compound (C) is preferably 0.001 to 3 ppm, more preferably 0.03 to 1 ppm. The content is particularly preferably 0.05 to 0.5 ppm.
If the content of the titanium compound (C) is too low, the effect of suppressing thermal deterioration will be reduced, and if the content is too high, thermal decomposition of the EVOH resin (A) will easily occur and coloration will occur.
ここで、一般的にEVOH樹脂は、熱によって劣化することが知られている。そのメカニズムは明らかではないが、熱劣化が進行するのは、前記反応の際にEVOH樹脂の主鎖に二重結合構造が生成し、この部位が反応起点となってさらに脱水反応を引き起して、EVOH樹脂の主鎖にポリエン構造が形成されるためと考えられる。 Here, it is generally known that EVOH resin deteriorates due to heat. Although the mechanism is not clear, the reason why thermal deterioration progresses is that a double bond structure is generated in the main chain of the EVOH resin during the above reaction, and this site becomes a reaction starting point, causing further dehydration reaction. This is thought to be due to the formation of a polyene structure in the main chain of the EVOH resin.
一方、EVOH樹脂組成物にチタン化合物を含有させた場合、チタンイオンにより、EVOH樹脂組成物が着色すると考えられるため、当業者であればチタン化合物の使用を避けることが技術常識である。 On the other hand, if the EVOH resin composition contains a titanium compound, it is thought that the EVOH resin composition will be colored by titanium ions, so it is common general knowledge for those skilled in the art to avoid the use of titanium compounds.
しかしながら、本発明では、このような技術常識に反して、ポリオレフィン系樹脂(B)と、特定微量のチタン化合物(C)とを組み合わせて用いた場合に、熱劣化が顕著に抑制されたEVOH樹脂組成物が得られることを見出したのである。 However, in the present invention, contrary to such common technical knowledge, we have developed an EVOH resin whose thermal deterioration is significantly suppressed when a polyolefin resin (B) and a specific trace amount of a titanium compound (C) are used in combination. They have found that a composition can be obtained.
すなわち、チタンは4価のイオンとして安定であり、微量であっても前記のようなEVOH樹脂の主鎖の二重結合に配位しキレートを形成する等して安定化するため、さらなるポリエン構造の形成を抑制しているものと推測される。また、ポリオレフィン系樹脂がチタン化合物と共存することによって、樹脂組成物内に二重結合部位が多数分布することになるため、さらなる二重結合の形成が抑制されて、熱安定性がより向上すると推測される。
一方で、チタン化合物(C)の含有量が多すぎると、チタン化合物(C)によりEVOH樹脂の熱分解が起こると考えられるため、本発明では、チタン化合物(C)の含有量を特定微量に限定している。
That is, titanium is stable as a tetravalent ion, and even if it is in a small amount, it coordinates with the double bond in the main chain of EVOH resin and stabilizes it by forming a chelate. It is assumed that this suppresses the formation of In addition, when polyolefin resin coexists with titanium compounds, many double bond sites are distributed within the resin composition, which suppresses the formation of further double bonds and further improves thermal stability. Guessed.
On the other hand, if the content of the titanium compound (C) is too large, it is thought that thermal decomposition of the EVOH resin will occur due to the titanium compound (C), so in the present invention, the content of the titanium compound (C) is reduced to a specific trace amount. Limited.
[その他の熱可塑性樹脂]
本EVOH樹脂組成物には、EVOH樹脂(A)及びポリオレフィン系樹脂(B)以外に、さらに樹脂成分として、他の熱可塑性樹脂を、本発明の効果を阻害しない範囲(例えば本EVOH樹脂組成物の通常30質量%以下、好ましくは20質量%以下、特に好ましくは10質量%以下)にて含有することができる。
[Other thermoplastic resins]
In addition to the EVOH resin (A) and the polyolefin resin (B), the present EVOH resin composition may contain other thermoplastic resins as resin components within a range that does not impede the effects of the present invention (for example, the present EVOH resin composition). (usually 30% by mass or less, preferably 20% by mass or less, particularly preferably 10% by mass or less).
他の熱可塑性樹脂としては、公知の熱可塑性樹脂を用いることができ、例えば、ポリエステル系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル系樹脂、ポリカーボネート系樹脂、ポリ塩化ビニリデン、ポリエステルエラストマー、ポリウレタンエラストマー、塩素化ポリエチレン、塩素化ポリプロピレン等があげられる。これらは単独でもしくは2種以上併せて用いることができる。 As other thermoplastic resins, known thermoplastic resins can be used, such as polyester resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, polyvinylidene chloride, polyester elastomers, polyurethane elastomers, and chlorine. Examples include chlorinated polyethylene and chlorinated polypropylene. These can be used alone or in combination of two or more.
[その他の配合剤]
また、本EVOH樹脂組成物には、本発明の効果を阻害しない範囲において、一般にEVOH樹脂に配合する配合剤が含有されていてもよい。前記配合剤としては、例えば、無機複塩(例えばハイドロタルサイト等)、可塑剤(例えばエチレングリコール、グリセリン、ヘキサンジオール等の脂肪族多価アルコール等)、酸素吸収剤[例えばアルミニウム粉、亜硫酸カリウム等の無機系酸素吸収剤;アスコルビン酸、さらにその脂肪酸エステルや金属塩等、没食子酸、水酸基含有フェノールアルデヒド樹脂等の多価フェノール類、テルペン化合物、三級水素含有樹脂と遷移金属とのブレンド物(例えば、ポリプロピレンとコバルトの組合せ)、炭素-炭素不飽和結合含有樹脂と遷移金属とのブレンド物(例えばポリブタジエンとコバルトの組合せ)、光酸化崩壊性樹脂(例えばポリケトン)、アントラキノン重合体(例えばポリビニルアントラキノン)等や、さらにこれらの配合物に光開始剤(ベンゾフェノン等)や、前記以外の酸化防止剤や消臭剤(活性炭等)を添加したもの等の高分子系酸素吸収剤]、熱安定剤、光安定剤、紫外線吸収剤、着色剤、帯電防止剤、界面活性剤(但し、滑剤として用いるものを除く)、抗菌剤、アンチブロッキング剤、充填材(例えば無機フィラー等)等を配合してもよい。これらの化合物は、単独でもしくは2種以上併せて用いることができる。
[Other combination agents]
Further, the present EVOH resin composition may contain additives that are generally blended into EVOH resins within a range that does not impede the effects of the present invention. Examples of the compounding agents include inorganic double salts (such as hydrotalcite), plasticizers (such as aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), and oxygen absorbers [such as aluminum powder and potassium sulfite]. Inorganic oxygen absorbers such as ascorbic acid, its fatty acid esters and metal salts, gallic acid, polyhydric phenols such as hydroxyl group-containing phenol aldehyde resin, terpene compounds, blends of tertiary hydrogen-containing resins and transition metals. (e.g., a combination of polypropylene and cobalt), blends of carbon-carbon unsaturated bond-containing resins and transition metals (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), etc., and polymeric oxygen absorbers such as those containing photoinitiators (benzophenone, etc.), antioxidants and deodorants (activated carbon, etc.) other than those mentioned above], thermally stable Contains additives, light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, anti-blocking agents, fillers (e.g. inorganic fillers, etc.). It's okay. These compounds can be used alone or in combination of two or more.
[EVOH樹脂組成物の製造方法]
本EVOH樹脂組成物は、前記必須成分であるEVOH樹脂(A)、ポリオレフィン系樹脂(B)及びチタン化合物(C)と、必要に応じて前記の各任意成分を用いて製造されるが、製造方法としては、例えば、ドライブレンド法、溶融混合法、溶液混合法、含浸法等の公知の方法があげられ、これらのなかでも、前記EVOH樹脂とチタン化合物とを含有する組成物原料を溶融混合する工程を備えることにより製造することが好ましい。また、これらの製造方法は、任意に組み合わせることも可能である。
[Method for manufacturing EVOH resin composition]
The present EVOH resin composition is manufactured using the EVOH resin (A), polyolefin resin (B), and titanium compound (C), which are the essential components, and each of the above-mentioned optional components as necessary. Examples of the method include known methods such as a dry blending method, a melt mixing method, a solution mixing method, and an impregnation method. It is preferable to manufacture by including a step of. Moreover, these manufacturing methods can also be combined arbitrarily.
前記ドライブレンド法としては、例えば、(I)EVOH樹脂(A)ペレットと、ポリオレフィン系樹脂(B)及びチタン化合物(C)とをタンブラー等を用いてドライブレンドする方法等があげられる。 Examples of the dry blending method include a method of dry blending (I) EVOH resin (A) pellets, polyolefin resin (B), and titanium compound (C) using a tumbler or the like.
前記溶融混合法としては、例えば、(II)EVOH樹脂(A)ペレットと、ポリオレフィン系樹脂(B)及びチタン化合物(C)のドライブレンド物を溶融混練して、ペレットや他の成形物を得る方法や、(III)溶融状態のEVOH樹脂(A)にポリオレフィン系樹脂(B)やチタン化合物(C)を添加して溶融混練し、ペレットや他の成形物を得る方法等があげられる。 As the melt mixing method, for example, (II) a dry blend of EVOH resin (A) pellets, polyolefin resin (B), and titanium compound (C) is melt-kneaded to obtain pellets or other molded products. and (III) a method in which polyolefin resin (B) and titanium compound (C) are added to molten EVOH resin (A) and melt-kneaded to obtain pellets or other molded products.
前記溶液混合法としては、例えば、(IV)EVOH樹脂(A)ペレットを用いて溶液を調製し、ここにポリオレフィン系樹脂(B)及び/又はチタン化合物(C)を配合し、凝固成形してペレット化し、固液分離して乾燥する方法や、(V)EVOH樹脂(A)の製造過程で、ケン化前のエチレン-ビニルエステル系共重合体溶液やケン化後のEVOH樹脂(A)の均一溶液(水/アルコール溶液等)にポリオレフィン系樹脂(B)及び/又はチタン化合物(C)を含有させた後、凝固成形してペレット化し、固液分離して乾燥する方法等があげられる。 As the solution mixing method, for example, (IV) a solution is prepared using EVOH resin (A) pellets, a polyolefin resin (B) and/or a titanium compound (C) is blended therein, and the mixture is coagulated and molded. In the method of pelletizing, solid-liquid separation and drying, and the manufacturing process of (V) EVOH resin (A), the ethylene-vinyl ester copolymer solution before saponification and the EVOH resin (A) after saponification are used. Examples include a method in which the polyolefin resin (B) and/or the titanium compound (C) are contained in a homogeneous solution (water/alcohol solution, etc.), then coagulated and formed into pellets, solid-liquid separated, and dried.
前記含浸法としては、例えば、(VI)EVOH樹脂(A)ペレットを、ポリオレフィン系樹脂(B)及び/又はチタン化合物(C)を含有する水溶液と接触させ、前記EVOH樹脂(A)ぺレット中にポリオレフィン系樹脂(B)及び/又はチタン化合物(C)を含浸させた後、乾燥する方法等をあげることができる。 As the impregnation method, for example, (VI) EVOH resin (A) pellets are brought into contact with an aqueous solution containing a polyolefin resin (B) and/or a titanium compound (C), and the EVOH resin (A) pellets are Examples include a method of impregnating a polyolefin resin (B) and/or a titanium compound (C) and then drying it.
また、前記の各方法においては、あらかじめEVOH樹脂(A)及び/又はポリオレフィン系樹脂(B)とチタン化合物(C)を所定割合で配合し、チタン化合物(C)の濃度の高い組成物(マスターバッチ)を作製し、かかる組成物(マスターバッチ)をEVOH樹脂(A)もしくはポリオレフィン系樹脂(B)と配合することにより、所望の濃度の樹脂組成物を得ることも可能である。 In addition, in each of the above methods, EVOH resin (A) and/or polyolefin resin (B) and titanium compound (C) are blended in a predetermined ratio in advance, and a composition with a high concentration of titanium compound (C) (master It is also possible to obtain a resin composition with a desired concentration by preparing a batch) and blending this composition (masterbatch) with an EVOH resin (A) or a polyolefin resin (B).
さらに本発明においては、前記の異なる手法を組み合わせることが可能である。なかでも、生産性や本発明の効果がより顕著な樹脂組成物が得られる点で、溶融混合法が好ましく、特には(II)の方法が好ましい。 Furthermore, in the present invention, it is possible to combine the different methods described above. Among these, the melt-mixing method is preferred, and the method (II) is particularly preferred, since a resin composition with more remarkable productivity and the effects of the present invention can be obtained.
なお、前記各方法によって得られる樹脂組成物のペレットや、前記各方法で用いられるEVOH樹脂(A)及び/又はポリアミド系樹脂(B)を含有するペレットの形状は任意であり、例えば、球形、オーバル形、円柱形、立方体形、直方体形等任意の形状が採用可能である。ペレットの形状は、通常、オーバル形又は円柱形であり、その大きさは、後に成形材料として用いる場合の利便性の観点から、円柱形の場合は底面の直径が通常1~6mm、好ましくは2~5mmであり、長さは通常1~6mm、好ましくは2~5mmである。オーバル形の場合は長径が通常1.5~30mm、好ましくは3~20mm、さらに好ましくは3.5~10mmである。短径は通常1~10mm、好ましくは2~6mmであり、特に好ましくは2.5~5.5mmである。かかる長径及び短径を測定する方法は、例えばペレットを手に取り観察し、ノギス等の計測器を用いて長径を測定した後に、かかる長径に垂直な断面のうち最大面積となる断面位置を目視及び触覚で認定し、かかる断面を想定した場合の短径を同様に測定する方法があげられる。 The pellets of the resin composition obtained by each of the above methods and the pellets containing EVOH resin (A) and/or polyamide resin (B) used in each of the above methods may have any shape, such as spherical, Any shape such as an oval shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, etc. can be adopted. The shape of the pellet is usually oval or cylindrical, and its size is such that the diameter of the bottom is usually 1 to 6 mm, preferably 2 mm, from the viewpoint of convenience when later used as a molding material. 5 mm, and the length is usually 1 to 6 mm, preferably 2 to 5 mm. In the case of an oval shape, the major axis is usually 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. The short axis is usually 1 to 10 mm, preferably 2 to 6 mm, particularly preferably 2.5 to 5.5 mm. The method of measuring the major axis and minor axis is, for example, by picking up the pellet, observing it, measuring the major axis using a measuring device such as a caliper, and then visually observing the position of the cross section that has the maximum area among the cross sections perpendicular to the major axis. Another method is to identify it by touch and similarly measure the short axis assuming such a cross section.
なお、本EVOH樹脂組成物の形状がペレットである場合、溶融成形時のフィード性を安定させる点で、ペレットの表面に公知の滑剤を付着させることが好ましい。滑剤の種類としては、例えば、炭素数12以上の高級脂肪酸(例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、オレイン酸等)、高級脂肪酸エステル(高級脂肪酸のメチルエステル、イソプロピルエステル、ブチルエステル、オクチルエステル等)、高級脂肪酸アミド(例えば、ラウリン酸アミド、ミリスチン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド等の飽和高級脂肪酸アミド;オレイン酸アミド、エルカ酸アミド等の不飽和高級脂肪酸アミド、エチレンビスステアリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、エチレンビスラウリン酸アミド等のビス高級脂肪酸アミド等)、低分子量ポリオレフィン(例えば分子量500~10000程度の低分子量ポリエチレン、又は低分子量ポリプロピレン等、又はその酸変性品)、炭素数6以上の高級アルコール、エステルオリゴマー、フッ化エチレン樹脂等があげられる。これらの化合物は、単独でもしくは2種以上併せて用いることができる。また、かかる滑剤の含有量は、本EVOH樹脂組成物の通常5質量%以下、好ましくは1質量%以下である。なお、下限は通常0質量%である。 In addition, when the present EVOH resin composition is in the form of pellets, it is preferable to attach a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Types of lubricants include, for example, higher fatty acids having 12 or more carbon atoms (for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (higher fatty acid methyl esters, isopropyl esters, butyl ester, octyl ester, etc.), higher fatty acid amides (for example, saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.); Bis-higher fatty acid amides such as saturated higher fatty acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, ethylene bis lauric acid amide, etc.), low molecular weight polyolefins (for example, low molecular weight of about 500 to 10,000) (polyethylene, low molecular weight polypropylene, etc., or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, fluorinated ethylene resins, etc. These compounds can be used alone or in combination of two or more. Further, the content of such a lubricant is usually 5% by mass or less, preferably 1% by mass or less of the EVOH resin composition. Note that the lower limit is usually 0% by mass.
このようにして得られる本EVOH樹脂組成物は、加熱時における熱劣化を抑制することができるものであり、本EVOH樹脂組成物の重量減少率は、通常1.8%以下であり、好ましくは1.6%以下であり、特に好ましくは1.5%以下である。前記重量減少率の下限は、低ければ低い程よい。
なお、前記重量減少率の0.1%の違いは、実際の製造において、大きな収率の差として現れることから、その差は非常に大きいものである。
The present EVOH resin composition obtained in this manner can suppress thermal deterioration during heating, and the weight loss rate of the present EVOH resin composition is usually 1.8% or less, preferably It is 1.6% or less, particularly preferably 1.5% or less. The lower the lower limit of the weight reduction rate, the better.
Note that the difference in weight reduction rate of 0.1% appears as a large difference in yield in actual production, so the difference is very large.
前記重量減少率は、本EVOH樹脂組成物のペレット5mgを、熱重量測定装置(Perkin Elmer社製、Pyris 1 TGA)を用いて、窒素雰囲気下、気流速度:20mL/分、温度:230℃、時間:1時間の条件下で重量を測定し、下記式により、求められるものである。
<式>
重量減少率(%)=[(加熱前重量-加熱後重量)/加熱前重量]×100
The weight loss rate was determined by measuring 5 mg of pellets of the present EVOH resin composition using a thermogravimeter (Pyris 1 TGA, manufactured by Perkin Elmer) under a nitrogen atmosphere, air flow rate: 20 mL/min, temperature: 230 ° C. The weight is measured under conditions of time: 1 hour, and is determined by the following formula.
<Formula>
Weight reduction rate (%) = [(weight before heating - weight after heating) / weight before heating] x 100
また、本EVOH樹脂組成物の含水率は、通常、0.01~0.5質量%であり、好ましくは0.05~0.35質量%、特に好ましくは0.1~0.3質量%である。 Further, the water content of the EVOH resin composition is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, particularly preferably 0.1 to 0.3% by mass. It is.
本EVOH樹脂組成物の含水率は、以下の方法により測定・算出されるものである。
本EVOH樹脂組成物の乾燥前質量(W1)を電子天秤にて秤量し、150℃の熱風乾燥機中で5時間乾燥させ、デシケーター中で30分間放冷後の質量(W2)を秤量し、下記の式より算出する。
<式>
含水率(質量%)=[(W1-W2)/W1]×100
The water content of the present EVOH resin composition is measured and calculated by the following method.
Weigh the mass (W 1 ) of the EVOH resin composition before drying using an electronic balance, dry it in a hot air dryer at 150°C for 5 hours, and weigh the mass (W 2 ) after leaving it to cool in a desiccator for 30 minutes. It is calculated using the formula below.
<Formula>
Moisture content (mass%) = [(W 1 - W 2 )/W 1 ] x 100
本EVOH樹脂組成物は、ペレットの他、粉末状や液体状といった、さまざまな形態に調製され、各種の成形物の成形材料として提供される。特に本発明においては、溶融成形用の材料として提供される場合、本発明の効果がより効率的に得られる傾向があり好ましい。
なお、本EVOH樹脂組成物には、本EVOH樹脂組成物に用いられるEVOH樹脂(A)及びポリアミド系樹脂(B)以外の樹脂を混合して得られる樹脂組成物も含まれる。
The present EVOH resin composition is prepared in various forms such as pellets, powder, and liquid, and is provided as a molding material for various molded products. In particular, in the present invention, it is preferable to provide the material as a material for melt molding, since the effects of the present invention tend to be more efficiently obtained.
Note that the present EVOH resin composition also includes a resin composition obtained by mixing resins other than the EVOH resin (A) and polyamide resin (B) used in the present EVOH resin composition.
前記成形物としては、例えば本EVOH樹脂組成物から成形された単層フィルムをはじめとして、本EVOH樹脂組成物からなる層を有する多層構造体等があげられる。 Examples of the molded product include a single layer film molded from the present EVOH resin composition, and a multilayer structure having layers made of the present EVOH resin composition.
[多層構造体]
本発明の一実施形態に係る多層構造体(以下、「本多層構造体」と称する)は、本EVOH樹脂組成物からなる層を備えるものである。本EVOH樹脂組成物からなる層(以下、単に「本EVOH樹脂組成物層」という)は、本EVOH樹脂組成物以外の熱可塑性樹脂を主成分とする他の基材(以下、基材に用いられる樹脂を「基材樹脂」と略記することがある)と積層することで、さらに強度を付与したり、本EVOH樹脂組成物層を水分等の影響から保護したり、他の機能を付与することができる。
[Multilayer structure]
A multilayer structure according to an embodiment of the present invention (hereinafter referred to as "this multilayer structure") includes a layer made of the present EVOH resin composition. A layer made of the present EVOH resin composition (hereinafter simply referred to as "the present EVOH resin composition layer") may be formed by using another base material (hereinafter referred to as a base material) containing a thermoplastic resin as a main component other than the present EVOH resin composition. (sometimes abbreviated as "base material resin"), the EVOH resin composition layer can be further strengthened, protected from the effects of moisture, etc., and provided with other functions. be able to.
前記基材樹脂としては、例えば、直鎖状低密度ポリエチレン、低密度ポリエチレン、超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、エチレン-プロピレン(ブロック及びランダム)共重合体、エチレン-α-オレフィン(炭素数4~20のα-オレフィン)共重合体等のポリエチレン系樹脂、ポリプロピレン、プロピレン-α-オレフィン(炭素数4~20のα-オレフィン)共重合体等のポリプロピレン系樹脂、ポリブテン、ポリペンテン、ポリ環状オレフィン系樹脂(環状オレフィン構造を主鎖及び側鎖の少なくとも一方を有する重合体)等の(未変性)ポリオレフィン系樹脂や、これらのポリオレフィン類を不飽和カルボン酸又はそのエステルでグラフト変性した不飽和カルボン酸変性ポリオレフィン系樹脂等の変性オレフィン系樹脂を含む広義のポリオレフィン系樹脂、アイオノマー、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸共重合体、エチレン-アクリル酸エステル共重合体、ポリエステル系樹脂、ポリアミド系樹脂(共重合ポリアミドも含む)、ポリ塩化ビニル、ポリ塩化ビニリデン、アクリル系樹脂、ポリスチレン系樹脂、ビニルエステル系樹脂、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、塩素化ポリエチレン、塩素化ポリプロピレン等のハロゲン化ポリオレフィン、芳香族又は脂肪族ポリケトン類等があげられる。これらは、単独でもしくは2種以上併せて用いることができる。 Examples of the base resin include linear low density polyethylene, low density polyethylene, very low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin. Polyethylene resins such as (α-olefin having 4 to 20 carbon atoms) copolymers, polypropylene, polypropylene resins such as propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers, polybutene, polypentene , (unmodified) polyolefin resins such as polycyclic olefin resins (polymers with a cyclic olefin structure having at least one of a main chain and a side chain), and graft modification of these polyolefins with unsaturated carboxylic acids or their esters. Broadly defined polyolefin resins including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, Polyester resin, polyamide resin (including copolyamide polyamide), polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, polystyrene elastomer, chlorinated Examples include halogenated polyolefins such as polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, and the like. These can be used alone or in combination of two or more.
これらのうち、疎水性樹脂である、ポリアミド系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリスチレン系樹脂が好ましく、より好ましくは、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリ環状オレフィン系樹脂及びこれらの不飽和カルボン酸変性ポリオレフィン系樹脂等のポリオレフィン系樹脂であり、特にポリ環状オレフィン系樹脂は、疎水性樹脂として好ましく用いられる。 Among these, hydrophobic resins such as polyamide resins, polyolefin resins, polyester resins, and polystyrene resins are preferable, and polyethylene resins, polypropylene resins, polycyclic olefin resins, and unsaturated resins thereof are more preferable. Polyolefin resins such as carboxylic acid-modified polyolefin resins, particularly polycyclic olefin resins, are preferably used as hydrophobic resins.
本多層構造体の層構成は、本EVOH樹脂組成物層をa(a1、a2、・・・)、基材樹脂層をb(b1、b2、・・・)とするとき、a/b、b/a/b、a/b/a、a1/a2/b、a/b1/b2、b2/b1/a/b1/b2、b2/b1/a/b1/a/b1/b2等、任意の組み合わせが可能である。また、該多層構造体を製造する過程で発生する端部や不良品等を再溶融成形して得られる、本EVOH樹脂組成物と本EVOH樹脂組成物以外の熱可塑性樹脂との混合物を含むリサイクル層をRとするとき、b/R/a、b/R/a/b、b/R/a/R/b、b/a/R/a/b、b/R/a/R/a/R/b等とすることも可能である。本多層構造体の層の数はのべ数にて通常2~15、好ましくは3~10である。前記の層構成において、それぞれの層間には、必要に応じて接着性樹脂を含有する接着性樹脂層を介在させてもよい。 The layer structure of the present multilayer structure is a/b, where the present EVOH resin composition layer is a (a1, a2, ...) and the base resin layer is b (b1, b2, ...). b/a/b, a/b/a, a1/a2/b, a/b1/b2, b2/b1/a/b1/b2, b2/b1/a/b1/a/b1/b2, etc., arbitrary A combination of these is possible. In addition, recycled products containing a mixture of the present EVOH resin composition and a thermoplastic resin other than the present EVOH resin composition obtained by remelting and molding the edges and defective products generated in the process of manufacturing the multilayer structure When the layer is R, b/R/a, b/R/a/b, b/R/a/R/b, b/a/R/a/b, b/R/a/R/a /R/b etc. is also possible. The total number of layers in the present multilayer structure is usually 2 to 15, preferably 3 to 10. In the above layered structure, an adhesive resin layer containing an adhesive resin may be interposed between each layer, if necessary.
前記接着性樹脂としては、公知のものを使用でき、基材樹脂層「b」に用いる熱可塑性樹脂の種類に応じて適宜選択すればよい。代表的には不飽和カルボン酸又はその無水物をポリオレフィン系樹脂に付加反応やグラフト反応等により化学的に結合させて得られるカルボキシ基を含有する変性ポリオレフィン系重合体をあげることができる。前記カルボキシ基を含有する変性ポリオレフィン系重合体としては、例えば、無水マレイン酸グラフト変性ポリエチレン、無水マレイン酸グラフト変性ポリプロピレン、無水マレイン酸グラフト変性エチレン-プロピレン(ブロック及びランダム)共重合体、無水マレイン酸グラフト変性エチレン-エチルアクリレート共重合体、無水マレイン酸グラフト変性エチレン-酢酸ビニル共重合体、無水マレイン酸変性ポリ環状オレフィン系樹脂、無水マレイン酸グラフト変性ポリオレフィン系樹脂等があげられる。これらは単独でもしくは2種以上を併せて用いてもよい。 As the adhesive resin, any known adhesive resin can be used, and may be appropriately selected depending on the type of thermoplastic resin used for the base resin layer "b". A typical example is a modified polyolefin polymer containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin by an addition reaction, a graft reaction, or the like. Examples of the modified polyolefin polymer containing a carboxyl group include maleic anhydride-grafted modified polyethylene, maleic anhydride-grafted modified polypropylene, maleic anhydride-grafted modified ethylene-propylene (block and random) copolymers, and maleic anhydride. Examples include graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft-modified ethylene-vinyl acetate copolymer, maleic anhydride-modified polycyclic olefin resin, maleic anhydride graft-modified polyolefin resin, and the like. These may be used alone or in combination of two or more.
本多層構造体において、本EVOH樹脂組成物層と基材樹脂層との間に、接着性樹脂層を用いる場合、接着性樹脂層が本EVOH樹脂組成物層の両側に位置することから、疎水性に優れた接着性樹脂を用いることが好ましい。 In this multilayer structure, when an adhesive resin layer is used between the present EVOH resin composition layer and the base resin layer, since the adhesive resin layer is located on both sides of the present EVOH resin composition layer, the hydrophobic It is preferable to use an adhesive resin with excellent properties.
前記基材樹脂、接着性樹脂には、本発明の趣旨を阻害しない範囲(例えば樹脂全体に対して、30質量%以下、好ましくは10質量%以下)において、従来知られているような可塑剤、フィラー、クレー(モンモリロナイト等)、着色剤、酸化防止剤、帯電防止剤、滑剤、核材、ブロッキング防止剤、ワックス等を含んでいてもよい。これらは単独でもしくは2種以上併せて用いることができる。 The base resin and the adhesive resin may contain a conventionally known plasticizer within a range that does not impede the spirit of the present invention (for example, 30% by mass or less, preferably 10% by mass or less based on the entire resin). , fillers, clays (such as montmorillonite), colorants, antioxidants, antistatic agents, lubricants, core materials, antiblocking agents, waxes, and the like. These can be used alone or in combination of two or more.
前記本EVOH樹脂組成物層と前記基材樹脂層との積層(接着性樹脂層を介在させる場合を含む)は、公知の方法にて行うことができる。例えば、本EVOH樹脂組成物のフィルム、シート等に基材樹脂を溶融押出ラミネートする方法、基材樹脂層に本EVOH樹脂組成物を溶融押出ラミネートする方法、本EVOH樹脂組成物と基材樹脂とを共押出する方法、本EVOH樹脂組成物(層)と基材樹脂(層)とを有機チタン化合物、イソシアネート化合物、ポリエステル系化合物、ポリウレタン化合物等の公知の接着剤を用いてドライラミネートする方法、基材樹脂上に本EVOH樹脂組成物の溶液を塗工してから溶媒を除去する方法等があげられる。これらのなかでも、コストや環境の観点から考慮して、本EVOH樹脂組成物層を溶融成形する工程を備えることにより製造することができる。具体的には共押出する方法が好ましい。 Lamination of the present EVOH resin composition layer and the base resin layer (including the case where an adhesive resin layer is interposed) can be performed by a known method. For example, a method of melt extrusion laminating a base resin on a film, sheet, etc. of the present EVOH resin composition, a method of melt extrusion laminating the present EVOH resin composition on a base resin layer, a method of melt extrusion laminating the present EVOH resin composition and a base resin, A method of dry laminating the present EVOH resin composition (layer) and a base resin (layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound. Examples include a method in which a solution of the present EVOH resin composition is applied onto the base resin and then the solvent is removed. Among these, in consideration from the viewpoint of cost and environment, the present EVOH resin composition layer can be manufactured by including a step of melt molding. Specifically, a coextrusion method is preferred.
本多層構造体は、必要に応じて(加熱)延伸処理を施してもよい。延伸処理は、一軸延伸、二軸延伸のいずれであってもよく、二軸延伸の場合は同時延伸であっても逐次延伸であってもよい。また、延伸方法としてはロール延伸法、テンター延伸法、チューブラー延伸法、延伸ブロー法、真空圧空成形等のうち延伸倍率の高いものも採用できる。延伸温度は、多層構造体の融点近傍の温度で、通常40~170℃、好ましくは60~160℃程度の範囲から選ばれる。延伸温度が低すぎる場合は延伸性が不良となり、高すぎる場合は安定した延伸状態を維持することが困難となる。 This multilayer structure may be subjected to (heating) stretching treatment if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, simultaneous stretching or sequential stretching may be performed. Further, as the stretching method, a method with a high stretching ratio among roll stretching methods, tenter stretching methods, tubular stretching methods, stretch blowing methods, vacuum-pressure forming, etc. can be adopted. The stretching temperature is selected from the range of usually 40 to 170°C, preferably about 60 to 160°C, near the melting point of the multilayer structure. If the stretching temperature is too low, the stretchability will be poor, and if it is too high, it will be difficult to maintain a stable stretched state.
また、延伸処理後の本多層構造体は、寸法安定性を付与することを目的として、熱固定を行ってもよい。熱固定は周知の手段で実施可能であり、例えば前記延伸処理された本多層構造体を、緊張状態を保ちながら通常80~180℃、好ましくは100~165℃で通常2~600秒間程度熱処理を行う。 Further, the present multilayer structure after the stretching treatment may be heat-set for the purpose of imparting dimensional stability. Heat fixation can be carried out by well-known means. For example, the stretched multilayer structure is heat-treated at a temperature of usually 80 to 180°C, preferably 100 to 165°C, for about 2 to 600 seconds while maintaining a tensioned state. conduct.
前記延伸処理された本多層構造体をシュリンク用フィルムとして用いる場合には、熱収縮性を付与するために、前記の熱固定を行わず、例えば延伸処理後の本多層構造体に冷風を当てて冷却固定する等の処理を行えばよい。 When the stretched multilayer structure is used as a shrink film, in order to impart heat shrinkability, the above heat setting is not performed, and the stretched multilayer structure is, for example, blown with cold air. Processing such as cooling and fixing may be performed.
本多層構造体(延伸したものを含む)の厚み、さらには多層構造体を構成する本EVOH樹脂組成物層、基材樹脂層及び接着性樹脂層の厚みは、層構成、基材樹脂の種類、接着性樹脂の種類、用途や包装形態、要求される物性等により一概にいえないが、本多層構造体(延伸したものを含む)の厚みは、通常10~5000μm、好ましくは30~3000μm、特に好ましくは50~2000μmである。本EVOH樹脂組成物層は通常1~500μm、好ましくは3~300μm、特に好ましくは5~200μmであり、基材樹脂層は通常5~3000μm、好ましくは10~2000μm、特に好ましくは20~1000μmであり、接着性樹脂層は、通常0.5~250μm、好ましくは1~150μm、特に好ましくは3~100μmである。 The thickness of the present multilayer structure (including the stretched one) and the thickness of the present EVOH resin composition layer, base resin layer, and adhesive resin layer that constitute the multilayer structure are determined by the layer structure and the type of base resin. The thickness of the present multilayer structure (including the stretched one) is usually 10 to 5000 μm, preferably 30 to 3000 μm, although it cannot be definitively stated depending on the type of adhesive resin, application, packaging form, required physical properties, etc. Particularly preferred is 50 to 2000 μm. The EVOH resin composition layer is usually 1 to 500 μm, preferably 3 to 300 μm, particularly preferably 5 to 200 μm, and the base resin layer is usually 5 to 3000 μm, preferably 10 to 2000 μm, particularly preferably 20 to 1000 μm. The adhesive resin layer has a thickness of usually 0.5 to 250 μm, preferably 1 to 150 μm, particularly preferably 3 to 100 μm.
さらに、本多層構造体における本EVOH樹脂組成物層の基材樹脂層に対する厚みの比(本EVOH樹脂組成物層/基材樹脂層)は、各層が複数ある場合は最も厚みの厚い層同士の比にて、通常1/99~50/50、好ましくは5/95~45/55、特に好ましくは10/90~40/60である。また、本多層構造体における本EVOH樹脂組成物層の接着性樹脂層に対する厚み比(本EVOH樹脂組成物層/接着性樹脂層)は、各層が複数ある場合は最も厚みの厚い層同士の比にて、通常10/90~99/1、好ましくは20/80~95/5、特に好ましくは50/50~90/10である。 Furthermore, in the present multilayer structure, the thickness ratio of the present EVOH resin composition layer to the base resin layer (present EVOH resin composition layer/base material resin layer) is the thickness ratio between the thickest layers when there is a plurality of each layer. The ratio is usually 1/99 to 50/50, preferably 5/95 to 45/55, particularly preferably 10/90 to 40/60. In addition, the thickness ratio of the present EVOH resin composition layer to the adhesive resin layer in the present multilayer structure (present EVOH resin composition layer/adhesive resin layer) is the ratio of the thickest layers when there is a plurality of each layer. The ratio is usually 10/90 to 99/1, preferably 20/80 to 95/5, particularly preferably 50/50 to 90/10.
また、本多層構造体を用いてカップやトレイ状の多層容器を得ることも可能である。その場合は、通常絞り成形法が採用され、具体的には真空成形法、圧空成形法、真空圧空成形法、プラグアシスト式真空圧空成形法等があげられる。さらに多層パリソン(ブロー前の中空管状の予備成形物)からチューブやボトル状の多層容器(積層体構造)を得る場合はブロー成形法が採用される。具体的には、押出ブロー成形法(双頭式、金型移動式、パリソンシフト式、ロータリー式、アキュムレーター式、水平パリソン式等)、コールドパリソン式ブロー成形法、射出ブロー成形法、二軸延伸ブロー成形法(押出式コールドパリソン二軸延伸ブロー成形法、射出式コールドパリソン二軸延伸ブロー成形法、射出成形インライン式二軸延伸ブロー成形法等)等があげられる。得られる積層体は必要に応じ、熱処理、冷却処理、圧延処理、印刷処理、ドライラミネート処理、溶液又は溶融コート処理、製袋加工、深絞り加工、箱加工、チューブ加工、スプリット加工等を行うことができる。 Moreover, it is also possible to obtain a multilayer container in the form of a cup or a tray using the present multilayer structure. In that case, a draw forming method is usually employed, and specific examples thereof include a vacuum forming method, a pressure forming method, a vacuum pressure forming method, a plug-assisted vacuum pressure forming method, and the like. Furthermore, when obtaining a tube or bottle-shaped multilayer container (laminate structure) from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specifically, extrusion blow molding methods (double-head type, moving mold type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, biaxial stretching Examples include blow molding methods (extrusion type cold parison biaxial stretch blow molding method, injection type cold parison biaxial stretch blow molding method, injection molding inline type biaxial stretch blow molding method, etc.). The obtained laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc. as necessary. I can do it.
そして、本多層構造体を用いて得られたフィルム、シート、延伸フィルムからなる袋及びカップ、トレイ、チューブ、ボトル等からなる容器や蓋材は、一般的な食品、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、飲料、化粧品、医薬品等の各種の包装材料容器として有用である。特に、本EVOH樹脂組成物として、機械的強度に優れたポリオレフィン系樹脂(B)を用いたものは、機械的強度に優れ、しかも熱劣化による着色等が抑制されている成形用樹脂材料であることから、高い機械的強度と美麗な外観が要求される包装用材料として、とりわけ有用である。また、繰り返し熱履歴を受けても熱安定性に優れていることから、再利用を前提とする包装用材料等としても、有用である。 Bags made of films, sheets, and stretched films obtained using this multilayer structure, as well as containers and lids made of cups, trays, tubes, bottles, etc., can be used for general foods, seasonings such as mayonnaise, dressing, etc. It is useful as a variety of packaging material containers for fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc. In particular, the present EVOH resin composition using a polyolefin resin (B) with excellent mechanical strength is a molding resin material that has excellent mechanical strength and is suppressed from discoloration due to thermal deterioration. Therefore, it is particularly useful as a packaging material that requires high mechanical strength and a beautiful appearance. Furthermore, since it has excellent thermal stability even after being subjected to repeated thermal history, it is useful as a packaging material etc. that is intended to be reused.
以下、実施例により本発明を具体的に説明する。但し、本発明は、以下の実施例により何ら限定されるものではない。
なお、例中「部」とあるのは、断りのない限り質量基準を意味する。
Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited in any way by the following examples.
In addition, "part" in the examples means a mass standard unless otherwise specified.
<実施例1>
EVOH樹脂(A)として、エチレン構造単位の含有量29モル%、ケン化度99.6モル%、MFR4g/10分(210℃、荷重2160g)のEVOH樹脂のペレットを用いた。
また、ポリオレフィン系樹脂(B)として、ポリプロピレン(日本ポリプロ社製、EA9、密度:0.90g/cm3)を用い、チタン化合物(C)として酸化チタン(富士フイルム和光純薬社製)を用いた。
<Example 1>
As the EVOH resin (A), pellets of an EVOH resin having an ethylene structural unit content of 29 mol %, a degree of saponification of 99.6 mol %, and an MFR of 4 g/10 minutes (210° C., load 2160 g) were used.
In addition, polypropylene (manufactured by Nippon Polypro Co., Ltd., EA9, density: 0.90 g/cm 3 ) was used as the polyolefin resin (B), and titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound (C). there was.
前記EVOH樹脂(A)のペレット150部と、前記ポリオレフィン系樹脂(B)2850部と、前記酸化チタンを金属換算含有量としてEVOH樹脂組成物の質量あたり0.01ppmとなるようにドライブレンドし、混合物を得た。そして、前記混合物を、二穴ダイを備えた二軸押出機(20mmφ)に供給し、下記の押出条件で押出、吐出されるストランドを水槽にて冷却、固化させた。つぎに、固化させたストランドに空気を吹き付けることでストランド表面の水滴を除去した後、切断することでEVOH樹脂組成物のペレットを得た。 150 parts of pellets of the EVOH resin (A), 2850 parts of the polyolefin resin (B), and the titanium oxide are dry blended so that the metal equivalent content is 0.01 ppm per mass of the EVOH resin composition, A mixture was obtained. The mixture was then supplied to a twin-screw extruder (20 mmφ) equipped with a two-hole die, extruded under the following extrusion conditions, and the extruded strand was cooled and solidified in a water tank. Next, water droplets on the surface of the strand were removed by blowing air onto the solidified strand, and then cut to obtain pellets of the EVOH resin composition.
[押出条件]
押出機設定温度(℃):C1/C2/C3/C4/C5/C6
=150/200/210/210/210/210
[Extrusion conditions]
Extruder setting temperature (℃): C1/C2/C3/C4/C5/C6
=150/200/210/210/210/210
<実施例2>
実施例1において、酸化チタンの配合量を金属換算量としてEVOH樹脂組成物の質量あたり0.083ppmに変更した以外は、実施例1と同様にしてEVOH樹脂組成物のペレットを得た。
<Example 2>
Pellets of an EVOH resin composition were obtained in the same manner as in Example 1, except that the amount of titanium oxide was changed to 0.083 ppm per mass of the EVOH resin composition in metal terms.
<比較例1>
実施例1において、酸化チタンを用いなかった以外は、実施例1と同様にしてEVOH樹脂組成物のペレットを得た。
<Comparative example 1>
Pellets of an EVOH resin composition were obtained in the same manner as in Example 1, except that titanium oxide was not used.
<比較例2>
実施例1において、酸化チタンの配合量を金属換算量としてEVOH樹脂組成物の質量あたり0.83ppmに変更した以外は、実施例1と同様にしてEVOH樹脂組成物のペレットを得た。
<Comparative example 2>
Pellets of an EVOH resin composition were obtained in the same manner as in Example 1, except that the amount of titanium oxide was changed to 0.83 ppm per mass of the EVOH resin composition in metal terms.
得られた実施例1、2、及び比較例1、2のEVOH樹脂組成物のペレットを用いて、下記の熱安定性評価を行った。結果を後記の表1に示す。 The following thermal stability evaluation was performed using the obtained pellets of the EVOH resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2. The results are shown in Table 1 below.
〔熱安定性評価〕
得られたEVOH樹脂組成物のペレットを5mg用い、熱重量測定装置(PerkinElmer社製、Pyris 1 TGA)により、窒素雰囲気下、気流速度:20mL/分、温度:230℃、時間:1時間の条件下での重量を測定し、下記の式により重量減少率を求めた。かかる値が低いほど、樹脂組成物が分解していないことを意味しており、樹脂組成物の熱安定性に優れることを意味する。
<式>
重量減少率(%)=[(加熱前重量-加熱後重量)/加熱前重量]×100
[Thermal stability evaluation]
Using 5 mg of the obtained pellets of the EVOH resin composition, the conditions were measured using a thermogravimetric analyzer (manufactured by PerkinElmer, Pyris 1 TGA) under nitrogen atmosphere, air flow rate: 20 mL/min, temperature: 230°C, time: 1 hour. The weight at the bottom was measured, and the weight loss rate was determined using the following formula. The lower the value, the less the resin composition is decomposed, and the better the thermal stability of the resin composition.
<Formula>
Weight reduction rate (%) = [(weight before heating - weight after heating) / weight before heating] x 100
前記表1から、ポリオレフィン系樹脂(B)と特定微量のチタン化合物(C)とを含有する実施例1、2のEVOH樹脂組成物は、チタン化合物(C)を含有しない比較例1のEVOH樹脂組成物、チタン化合物(C)を特定の範囲よりも多量に含有する比較例2のEVOH樹脂組成物に比べて、重量変化が小さく、熱安定性に優れることがわかる。
また、実施例1、2のEVOH樹脂組成物からなる層を備える多層構造体も、熱劣化が抑制され熱安定性に優れるものである。
From Table 1 above, the EVOH resin compositions of Examples 1 and 2 containing a polyolefin resin (B) and a specific trace amount of a titanium compound (C) are different from the EVOH resin of Comparative Example 1 containing no titanium compound (C). It can be seen that the composition shows a small change in weight and has excellent thermal stability compared to the EVOH resin composition of Comparative Example 2 containing titanium compound (C) in an amount larger than the specific range.
Further, the multilayer structure including the layers made of the EVOH resin compositions of Examples 1 and 2 also has excellent thermal stability with suppressed thermal deterioration.
本EVOH樹脂組成物は、溶融成形等の加熱時において熱劣化が抑制されることから、各種食品の他、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、水、飲料、化粧品、医薬品等の各種包装材料として、有用である。 This EVOH resin composition suppresses thermal deterioration during heating during melt molding, etc., so it can be used in various foods, seasonings such as mayonnaise and dressing, fermented foods such as miso, oil and fat foods such as salad oil, water, etc. It is useful as a variety of packaging materials for beverages, cosmetics, pharmaceuticals, etc.
Claims (8)
前記チタン化合物(C)の金属換算含有量が、エチレン-ビニルアルコール系共重合体組成物の質量あたり0.00005ppm以上0.5ppm未満であるエチレン-ビニルアルコール系共重合体組成物。 An ethylene-vinyl alcohol copolymer composition containing an ethylene-vinyl alcohol copolymer (A), a polyolefin resin (B), and a titanium compound (C),
An ethylene-vinyl alcohol copolymer composition in which the content of the titanium compound (C) in terms of metal is 0.00005 ppm or more and less than 0.5 ppm per mass of the ethylene-vinyl alcohol copolymer composition.
前記エチレン-ビニルアルコール系共重合体とチタン化合物とを含有する組成物原料を溶融混合する工程を備える、エチレン-ビニルアルコール系共重合体組成物の製造方法。 A method for producing the ethylene-vinyl alcohol copolymer composition according to claim 1 or 2, comprising:
A method for producing an ethylene-vinyl alcohol copolymer composition, comprising the step of melt-mixing composition raw materials containing the ethylene-vinyl alcohol copolymer and a titanium compound.
前記エチレン-ビニルアルコール系共重合体組成物からなる層を溶融成形する工程を備える、多層構造体の製造方法。 A method for manufacturing the multilayer structure according to claim 6, comprising:
A method for producing a multilayer structure, comprising the step of melt-molding a layer made of the ethylene-vinyl alcohol copolymer composition.
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