JPH06136206A - Acid-modified polyolefinic resin composition and adhesive film or sheet obtained by using the same - Google Patents

Acid-modified polyolefinic resin composition and adhesive film or sheet obtained by using the same

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Publication number
JPH06136206A
JPH06136206A JP4287913A JP28791392A JPH06136206A JP H06136206 A JPH06136206 A JP H06136206A JP 4287913 A JP4287913 A JP 4287913A JP 28791392 A JP28791392 A JP 28791392A JP H06136206 A JPH06136206 A JP H06136206A
Authority
JP
Japan
Prior art keywords
acid
modified polyolefin
ethylene
resin
resin composition
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
Application number
JP4287913A
Other languages
Japanese (ja)
Other versions
JP3232317B2 (en
Inventor
Toshio Fujii
敏雄 藤井
Kazuhiro Kato
和広 加藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Kasei Corp
Original Assignee
Mitsubishi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Priority to JP28791392A priority Critical patent/JP3232317B2/en
Publication of JPH06136206A publication Critical patent/JPH06136206A/en
Application granted granted Critical
Publication of JP3232317B2 publication Critical patent/JP3232317B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To obtain a polyolefinic resin composition, excellent in transparency and capable of producing a adhesive film or sheet by melt mixing an acid- modified polyolefinic resin with an ethylene-vinyl alcohol copolymer resin under specific conditions. CONSTITUTION:This acid-modified polyolefinic resin composition is obtained by melt mixing (A) preferably 60-98wt.% acid-modified polyolefinic resin prepared by melt kneading a polyolefin with unsaturated carboxylic acids (preferably maleic anhydride) and an organic peroxide with an extruder, etc., in which 2-50wt.% thereof is preferably an acid-modified elastomer with (B) 2-40wt.% ethylene-vinyl alcohol copolymer resin having preferably 1-10g/10min, especially 2-7g/10min MFR and preferably 20-60mol% ethylene content, especially 25-50mol% ethylene content under conditions so as to provide >=0.3kW.hr/kg, preferably 0.4-2kW.hr/kg specific energy relatively to the resin. Furthermore, this adhesive sheet or film is prepared by molding the acid-modified polyolefinic resin composition.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、各種基材、特に、ポリ
オレフィンやエチレン−ビニルアルコール共重合樹脂
（以下ＥＶＯＨと呼ぶ時もある。）等との接着性が良好
な酸変性ポリオレフィン樹脂組成物および該組成物を成
形して得られる透明性に優れた接着性フィルム又はシー
トに関するものである。FIELD OF THE INVENTION The present invention relates to an acid-modified polyolefin resin composition having good adhesion to various substrates, particularly polyolefins and ethylene-vinyl alcohol copolymer resins (hereinafter sometimes referred to as EVOH). And an adhesive film or sheet having excellent transparency, which is obtained by molding the composition.

【０００２】[0002]

【従来の技術】一般に、ポリオレフィンは機械的性質、
透明性、成形性、衛生性等に優れているため広い分野に
わたって使用されている。しかし、積層体としての利用
を考えた場合、ポリオレフィンは無極性のためＥＶＯＨ
の様な極性物質との接着性が悪く、これを改良するため
種々の改質が行われている。例えば、極性物質をブレン
ドしたり、極性モノマーをグラフト反応させることが試
みられているが、まだ接着性は充分とは言えない。その
ため、接着性を更に改良するために、例えば不飽和カル
ボン酸或いはその誘導体をグラフトした変性ポリオレフ
ィン樹脂（以下単に「酸変性ポリオレフィン樹脂」とも
いう）にエチレン−プロピレン共重合体等のゴム物質や
低密度ポリエチレン等を混合した酸変性ポリオレフィン
樹脂組成物を用いる方法が提案されている（特公昭５４
−４０１１２号、同５４−４０１１３号）。BACKGROUND OF THE INVENTION Generally, polyolefins have mechanical properties,
It is used in a wide range of fields due to its excellent transparency, moldability and hygiene. However, when considering its use as a laminate, polyolefin is non-polar, so EVOH
Adhesiveness with polar substances such as that described above is poor, and various modifications have been made to improve this. For example, attempts have been made to blend polar substances or to carry out a graft reaction with polar monomers, but the adhesiveness is still insufficient. Therefore, in order to further improve the adhesiveness, for example, a modified polyolefin resin grafted with an unsaturated carboxylic acid or a derivative thereof (hereinafter also simply referred to as an “acid-modified polyolefin resin”) is added to a rubber substance such as an ethylene-propylene copolymer or a low-molecular compound. A method using an acid-modified polyolefin resin composition mixed with high-density polyethylene or the like has been proposed (Japanese Patent Publication No. 54-54).
-40112, 54-40113).

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、上記の
様にして製造された酸変性ポリオレフィン樹脂組成物
は、ある程度の接着性の改良効果はあるが、その効果は
まだ十分でなく、例えばシュリンク包装用途の場合、フ
ィルムを加熱収縮させた時に高収縮率条件では白化した
りする問題があり、改良が望まれていた。However, although the acid-modified polyolefin resin composition produced as described above has a certain degree of improving effect on the adhesiveness, the effect is not yet sufficient. For example, shrink packaging applications. In this case, there is a problem that whitening occurs when the film is heated and shrunk under a high shrinkage ratio condition, and improvement has been desired.

【０００４】[0004]

【課題を解決するための手段】本発明者らは、酸変性ポ
リオレフィン樹脂の接着性を向上させ、しかも、フィル
ムまたはシートに成形したときの透明性が良好な組成物
を提供すべく、種々の添加剤を検討した中からエチレン
−ビニルアルコール共重合樹脂を配合することに着目し
た。即ち、酸変性ポリオレフィン樹脂にＥＶＯＨを適当
量配合させる事で接着性が大幅に向上する事を見い出し
た。DISCLOSURE OF THE INVENTION In order to provide a composition which improves the adhesiveness of an acid-modified polyolefin resin and has good transparency when formed into a film or sheet, the present inventors have From the study of additives, attention was paid to blending an ethylene-vinyl alcohol copolymer resin. That is, it has been found that the adhesiveness is significantly improved by blending an acid-modified polyolefin resin with an appropriate amount of EVOH.

【０００５】しかも、酸変性ポリオレフィン樹脂に適当
量の酸変性ポリオレフィンエラストマーを含んでいると
接着性がより改善される事を知得し、更には酸変性ポリ
オレフィン樹脂とＥＶＯＨを溶融混合させる際に比エネ
ルギーが０．３ｋＷ・ｈｒ／ｋｇ以上の条件下で行なう
事で透明性も改善される事を見い出し本発明を完成する
に至った。即ち本発明の要旨は酸変性ポリオレフィン樹
脂６０〜９８重量％とエチレン−ビニルアルコール共重
合樹脂２〜４０重量％を溶融混合して得た酸変性ポリオ
レフィン樹脂組成物及び該組成物を成形して得た接着性
フィルム又はシートに存する。Moreover, it is known that the acid-modified polyolefin resin contains an appropriate amount of the acid-modified polyolefin elastomer to improve the adhesiveness, and further, when the acid-modified polyolefin resin and EVOH are melt-mixed, The inventors have found that the transparency is improved by carrying out the treatment under the condition of energy of 0.3 kW · hr / kg or more, and completed the present invention. That is, the gist of the present invention is to obtain an acid-modified polyolefin resin composition obtained by melt-mixing 60 to 98% by weight of an acid-modified polyolefin resin and 2 to 40% by weight of an ethylene-vinyl alcohol copolymer resin, and molding the composition. And an adhesive film or sheet.

【０００６】以下本発明を説明する。本発明の組成物に
おける酸変性ポリオレフィン樹脂は、任意の方法によ
り、ポリプロピレン及び／またはポリエチレン等に不飽
和カルボン酸またはその誘導体をグラフト反応させるこ
とにより得られる。例えば、ポリオレフィンと不飽和カ
ルボン酸類とを、溶融状態で反応させる方法（例えば特
公昭４３−２７４２１号）、溶液状態で反応させる方法
（例えば特公昭４４−１５４２２号）、スラリー状態で
反応させる方法（例えば特公昭４３−１８１４４号）、
気相状態で反応させる方法（例えば特開昭５０−７７４
９３号）などがある。これらの方法の中で押出機を用い
る溶融混練法が操作上簡便であるため好ましく用いられ
る。The present invention will be described below. The acid-modified polyolefin resin in the composition of the present invention can be obtained by graft-reacting polypropylene and / or polyethylene or the like with an unsaturated carboxylic acid or its derivative by any method. For example, a method of reacting a polyolefin with an unsaturated carboxylic acid in a molten state (for example, JP-B-43-27421), a method of reacting in a solution state (for example, JP-B-44-15422), a method of reacting in a slurry state ( For example, Japanese Patent Publication No. 43-18144),
A method of reacting in a gas phase (for example, JP-A-50-774).
No. 93) and so on. Among these methods, the melt-kneading method using an extruder is preferable because it is simple in operation.

【０００７】酸変性ポリオレフィン樹脂の原料として
は、例えば、ポリプロピレンやポリエチレンのホモポリ
マーおよびコポリマーが使用される。コポリマーとして
は、プロピレンと１〜５重量％のエチレンとのランダム
またはブロック共重合体、エチレンと、１〜１０重量％
のプロピレンとのランダムまたはブロック共重合体、プ
ロピレンまたはエチレンと１〜１０重量％のＣ4 以上の
α−オレフィンとの共重合体、およびこれらの混合物等
が用いられる。これらのうち特にメルトフローインデッ
クス（以下単にＭＦＩと略記する）が０．５乃至３０ｇ
／１０分、特に、５乃至１５ｇ／１０分のホモポリプロ
ピレンおよびプロピレン−エチレンランダム共重合体又
は、ＭＦＩが０．３乃至３０ｇ／１０分のポリエチレン
及びエチレン−αオレフィン共重合体が好ましく用いら
れる。As the raw material for the acid-modified polyolefin resin, for example, homopolymers and copolymers of polypropylene and polyethylene are used. As the copolymer, a random or block copolymer of propylene and 1 to 5% by weight of ethylene, and 1 to 10% by weight of ethylene
A random or block copolymer with propylene, a copolymer of propylene or ethylene with 1 to 10% by weight of C 4 or more α-olefin, and a mixture thereof. Among these, especially the melt flow index (hereinafter abbreviated as MFI) is 0.5 to 30 g.
/ 10 minutes, particularly 5 to 15 g / 10 minutes of homopolypropylene and propylene-ethylene random copolymer or polyethylene and ethylene-α-olefin copolymer having MFI of 0.3 to 30 g / 10 minutes are preferably used.

【０００８】ここでいうＭＦＩとはＡＳＴＭ−Ｄ１２３
８の規格に基づきポリプロピレンの場合２３０℃、ポリ
エチレンの場合１９０℃で測定した値である。また、不
飽和カルボン酸類としては、例えばアクリル酸、メタク
リル酸、マレイン酸、フマル酸、イタコン酸、シトラコ
ン酸、またそれら酸無水物、エステル、アミド、イミ
ド、金属塩等であり、これらのうち、無水マレイン酸を
用いるのが最も好ましい。The MFI mentioned here is ASTM-D123.
The values are measured at 230 ° C. for polypropylene and 190 ° C. for polyethylene based on the standard of 8. The unsaturated carboxylic acids include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and their acid anhydrides, esters, amides, imides, metal salts, and the like. Most preferably, maleic anhydride is used.

【０００９】またポリオレフィンと不飽和カルボン酸類
との反応を促進するために有機過酸化物が用いられる。
有機過酸化物としては、例えば、ベンゾイルパーオキサ
イド、ラウロイルパーオキサイド、アゾビスイソブチロ
ニトリル、ジクミルパーオキサイド、α，α′−ビス
（ｔ−ブチルパーオキシジイソプロピル）ベンゼン、
２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブ
チルパーオキシ）ヘキシン−３、ジ−ｔ−ブチルパーオ
キサイド、クメンヒドロパーオキサイド、ｔ−ブチルヒ
ドロパーオキサイドなどが挙げられる。有機過酸化物の
添加量は特に制限されないが、ポリオレフィン１００重
量部に対して通常０．００５乃至５重量部、好ましくは
０．０１乃至１重量部である。Further, an organic peroxide is used to accelerate the reaction between the polyolefin and the unsaturated carboxylic acid.
Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α, α′-bis (t-butylperoxydiisopropyl) benzene,
2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide, Cumene hydroperoxide, t-butyl hydroperoxide and the like can be mentioned. The amount of the organic peroxide added is not particularly limited, but is usually 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the polyolefin.

【００１０】不飽和カルボン酸類をグラフトした酸変性
ポリオレフィン樹脂は、上記に示したポリオレフィン、
不飽和カルボン酸類、有機過酸化物をタンブラー、ヘン
シエルミキサー等で充分に混合し、ポリオレフィンの融
点以上、一般には融点以上２８０℃以下の温度で溶融混
練してグラフト化反応を行なわせる。溶融混練する方法
は特に制限されず、例えばスクリュー押出機、バンバリ
ーミキサー、ミキシングロールなどを用いて行うことが
できるが、操作の簡便さのためスクリュー押出機が好ま
しく使用される。溶融混練の温度および時間は用いる有
機過酸化物の分解温度により変化するが、一般に１６０
乃至２８０℃で０．３乃至３０分間、好ましくは１７０
乃至２５０℃で１乃至１０分間が適当である。The acid-modified polyolefin resin grafted with unsaturated carboxylic acids is the polyolefin shown above,
Unsaturated carboxylic acids and organic peroxides are thoroughly mixed with a tumbler, a Henschel mixer or the like, and melt-kneaded at a temperature not lower than the melting point of the polyolefin, generally not lower than the melting point and not higher than 280 ° C to carry out a grafting reaction. The method of melt-kneading is not particularly limited, and for example, a screw extruder, a Banbury mixer, a mixing roll or the like can be used, but a screw extruder is preferably used because of the ease of operation. The temperature and time of melt-kneading vary depending on the decomposition temperature of the organic peroxide used, but generally 160
To 280 ° C. for 0.3 to 30 minutes, preferably 170
It is suitable to be at 1 to 10 minutes at 1 to 250 ° C.

【００１１】本発明においては、上記酸変性ポリオレフ
ィン樹脂は少なくとも２重量％以上、好ましくは３〜５
０重量％、特に好ましくは、５〜２５重量％の酸変性ポ
リオレフィンエラストマーを含有した方がより良好な接
着性が得られる。酸変性ポリオレフィンエラストマーの
原料としては、例えば、エチレンと炭素数３以上のα−
オレフィンとの共重合エラストマーが使用される。中で
も、密度が０．９１ｇ／ｃｍ3 未満、好ましくは０．８
５〜０．９０ｇ／ｃｍ3 で、メルトフローシレオ（ＭＦ
Ｒ）が０．１〜５０ｇ／１０分（ＡＳＴＭ−Ｄ１２３
８、１９０℃）、好ましくは、１〜２０ｇ／１０分のも
のが好適である。エチレンと共重合させる炭素数３以上
のα−オレフィンとしてはプロピレン、１−ブテン、１
−ペンテン、１−ヘキセン、４−メチル−１−ペンテン
等が挙げられ、これらと共に１，４−ヘキサジエン、ジ
シクロペンタジエン、エチリデンノルボルネン等の非共
役ジエンを使用することもできる。In the present invention, the above acid-modified polyolefin resin is at least 2% by weight, preferably 3-5.
Better adhesion is obtained by containing 0% by weight, particularly preferably 5 to 25% by weight of acid-modified polyolefin elastomer. Examples of the raw material of the acid-modified polyolefin elastomer include ethylene and α- having 3 or more carbon atoms.
Copolymerized elastomers with olefins are used. Above all, the density is less than 0.91 g / cm 3 , preferably 0.8.
Melt flow silo (MF at 5 to 0.90 g / cm 3
R) is 0.1 to 50 g / 10 minutes (ASTM-D123
8, 190 ° C.), preferably 1 to 20 g / 10 minutes. The α-olefin having 3 or more carbon atoms to be copolymerized with ethylene is propylene, 1-butene, 1
-Pentene, 1-hexene, 4-methyl-1-pentene and the like can be mentioned, and non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene and ethylidene norbornene can also be used with them.

【００１２】上記エチレン−α−オレフィン共重合エラ
ストマーは、チーグラー型触媒、中でもオキシ三塩化バ
ナジウム、四塩化バナジウム等のバナジウム化合物と有
機アルミニウム化合物とからなる触媒を用いて、エチレ
ンとα−オレフィンとを共重合させることにより製造す
ることができ、エラストマー中のエチレン含有量が４０
〜９０モル％の範囲であり、α−オレフィンの含有量が
１０〜６０モル％の範囲であるのが望ましい。上記エチ
レン−α−オレフィン共重合エラストマーの市販品とし
ては、例えば、ＣｄＦ Ｃｈｉｍｉｅ Ｅ．Ｐ．社のＮ
ＯＲＳＯＦＬＥＸ（ＦＷ１６００，ＦＷ１９００，ＭＷ
１９２０，ＳＭＷ２４４０，ＬＷ２２２０，ＬＷ２５０
０，ＬＷ２５５０）；日本ユニカーのフレックスレジン
（ＤＦＤＡ１１３７，ＤＦＤＡ１１３８，ＤＥＦＤ１２
１０，ＤＥＦＤ９０４２）；三井石油化学社のタフマー
（Ａ４０８５，Ａ４０９０，Ｐ０１８０，Ｐ０４８
０）、日本合成ゴム社のＪＳＲ−ＥＰ（ＥＰ０２Ｐ，Ｅ
Ｐ０７Ｐ，ＥＰ５７Ｐ）などが挙げられる。The above ethylene-α-olefin copolymer elastomer is obtained by using a Ziegler type catalyst, especially a vanadium compound such as vanadium oxytrichloride, vanadium tetrachloride and the like, and an organoaluminum compound to produce ethylene and α-olefin. It can be produced by copolymerization, and the ethylene content in the elastomer is 40
To 90 mol%, and the content of α-olefin is preferably 10 to 60 mol%. Examples of commercially available ethylene-α-olefin copolymer elastomers include CdF Chimie E. P. Company N
ORSOFLEX (FW1600, FW1900, MW
1920, SMW2440, LW2220, LW250
0, LW2550); Nippon Unicar Flex Resin (DFDA1137, DFDA1138, DEFD12)
10, DEFD9042); Tuffmer (A4085, A4090, P0180, P048) of Mitsui Petrochemical Co., Ltd.
0), JSR-EP (EP02P, E of Japan Synthetic Rubber Co., Ltd.)
P07P, EP57P) and the like.

【００１３】これらエラストマーの酸変性は、上述のポ
リオレフィン樹脂の酸変性と同様に行うことができる。
本発明においては、未変性のポリオレフィン樹脂とエラ
ストマーを混練しながら同時に酸変性処理を施してもよ
い。酸変性ポリオレフィン樹脂（酸変性ポリオレフィン
エラストマーを用いる場合はこれを含む）中の不飽和カ
ルボン酸類のグラフト量は０．０１〜３重量％、好まし
くは０．０３〜１重量％である。不飽和カルボン酸類の
グラフト量が０．０１重量％以下では接着性が低下し、
３重量％以上ではゲル化物が増大し易くなるため好まし
くない。The acid modification of these elastomers can be carried out in the same manner as the acid modification of the above-mentioned polyolefin resin.
In the present invention, the acid modification treatment may be simultaneously performed while kneading the unmodified polyolefin resin and the elastomer. The graft amount of the unsaturated carboxylic acids in the acid-modified polyolefin resin (including the acid-modified polyolefin elastomer when used) is 0.01 to 3% by weight, preferably 0.03 to 1% by weight. When the graft amount of unsaturated carboxylic acids is 0.01% by weight or less, the adhesiveness is lowered,
If it is 3% by weight or more, the gelled product tends to increase, which is not preferable.

【００１４】また、本発明においては、酸変性ポリオレ
フィン樹脂１００重量部に対して、最大２０００重量部
までの未変性ポリオレフィン樹脂を混合してもよい。そ
の際、最終混合物中の不飽和カルボン酸類のグラフト量
が上記範囲内になるように混合するのがよい。かかる未
変性ポリオレフィン樹脂としては、上述した酸変性ポリ
オレフィン樹脂の原料であるポリプロピレンやポリエチ
レンが挙げられる。In the present invention, up to 2000 parts by weight of unmodified polyolefin resin may be mixed with 100 parts by weight of acid-modified polyolefin resin. At that time, it is preferable to mix the unsaturated carboxylic acids in the final mixture so that the grafted amount is within the above range. Examples of the unmodified polyolefin resin include polypropylene and polyethylene, which are raw materials of the acid-modified polyolefin resin described above.

【００１５】上記酸変性ポリオレフィン樹脂に混合する
エチレン−ビニルアルコール共重合樹脂としては通常Ｍ
ＦＲが１〜２０ｇ／１０分（２３０℃）のものが使用さ
れる。酸変性ポリオレフィンとの相溶性や成形性の観点
から好ましくはＭＦＲが１〜１０ｇ／１０分、より好ま
しくは２〜７ｇ／１０分のものが望ましい。ＭＦＲが１
ｇ／１０分未満では相溶性、押出性が悪く、逆に２０ｇ
／１０分を越えると相溶性、成膜安定性が低下する。更
にエチレン−ビニルアルコール共重合樹脂中のエチレン
含有量も性能に大きく影響し、好ましくはエチレンが２
０〜６０モル％、より好ましくは２５〜５０モル％が望
ましい。The ethylene-vinyl alcohol copolymer resin to be mixed with the above acid-modified polyolefin resin is usually M
The one having FR of 1 to 20 g / 10 minutes (230 ° C.) is used. From the viewpoint of compatibility with the acid-modified polyolefin and moldability, the MFR is preferably 1 to 10 g / 10 minutes, more preferably 2 to 7 g / 10 minutes. MFR is 1
If it is less than 10 minutes, the compatibility and extrudability are poor, and conversely 20 g.
If it exceeds / 10 minutes, the compatibility and the film-forming stability deteriorate. Further, the ethylene content in the ethylene-vinyl alcohol copolymer resin also has a great influence on the performance.
0 to 60 mol%, more preferably 25 to 50 mol% is desirable.

【００１６】含有量が２０モル％未満では耐水性、押出
性に問題を生じ、逆に５０モル％を越えると相溶性が低
下する。酸変性ポリオレフィン樹脂とＥＶＯＨ樹脂との
混合は、樹脂に対する比エネルギー０．３ｋＷ・ｈｒ／
ｋｇ以上、好ましくは、０．４〜２．０ｋＷ・ｈｒ／ｋ
ｇ、特に好ましくは、０．５〜１．５ｋＷ・ｈｒ／ｋｇ
の条件に溶融混合するのが好ましい。例えば、酸変性ポ
リオレフィン樹脂とＥＶＯＨ樹脂とを、上記条件で、１
９０〜３５０℃でスクリュー押出機、バンバリーミキサ
ー、ミキシングロール等で溶融混合する。If the content is less than 20 mol%, problems occur in water resistance and extrudability, and if it exceeds 50 mol%, the compatibility decreases. Mixing acid-modified polyolefin resin and EVOH resin has a specific energy of 0.3 kW · hr /
kg or more, preferably 0.4 to 2.0 kW · hr / k
g, particularly preferably 0.5 to 1.5 kW · hr / kg
It is preferable to melt-mix under the conditions of. For example, acid-modified polyolefin resin and EVOH resin are
Melt and mix at 90 to 350 ° C. with a screw extruder, Banbury mixer, mixing roll, or the like.

【００１７】ここで比エネルギーとは、樹脂を溶融混練
する際に、単位重量当り（１ｋｇ）の樹脂に混練設備か
ら混練の効果の為に与えられるエネルギーをいい、数値
が大きい場合が練りの効果が高い事になる。例えば押出
機の場合、１ｋｇの樹脂を押し出すのに必要なスクリュ
ー駆動用モーターの消費電力で近似的に表わされる。ま
たバンバリーミキサー等のロール式混練機の場合は、樹
脂１ｋｇ処理するのに必要なロールの駆動用モーターの
消費電力で近似的に表わされる。Here, the specific energy means the energy given to the resin per unit weight (1 kg) from the kneading equipment for the effect of kneading when the resin is melt-kneaded, and when the value is large, the kneading effect is obtained. Will be high. For example, in the case of an extruder, it is approximately represented by the power consumption of a screw driving motor required to extrude 1 kg of resin. In the case of a roll-type kneader such as a Banbury mixer, it can be approximately represented by the power consumption of a roll driving motor required for treating 1 kg of resin.

【００１８】具体的には、押出機のモーターに電流計、
電圧計等を取り付け、これからモーターの電力消費量を
得、これにモーターの力率（通常０．８５程度）を掛
け、１ｋｇの樹脂に加えられる混練力（ｋＷ・ｈｒ／ｋ
ｇ）を得る。ＥＶＯＨ樹脂は、得られる樹脂組成物中、
２〜４０重量％、好ましくは、１０〜２５重量％となる
ように混合する。これらの範囲外だと接着性、透明性の
改良効果が低下するのであまり好ましくない。Specifically, the motor of the extruder is equipped with an ammeter,
Attach a voltmeter, etc. to obtain the power consumption of the motor, multiply it by the power factor of the motor (usually about 0.85), and add the kneading power (kW · hr / k) to 1 kg of resin.
g) is obtained. EVOH resin is a resin composition obtained by
2 to 40% by weight, preferably 10 to 25% by weight are mixed. If it is out of these ranges, the effect of improving the adhesiveness and the transparency is deteriorated, which is not so preferable.

【００１９】本発明の酸変性ポリオレフィン組成物に
は、通常使用する程度の耐熱安定剤、耐候安定剤、滑
剤、帯電防止剤、核剤、充填剤、顔料、染料、難燃剤、
ブロッキング防止剤等の添加物を０．０００５〜３０重
量％程度含有させてもよい。かくして得られる本発明の
酸変性ポリオレフィン樹脂組成物を、常法に従い成形す
ることによって、接着性が良好で、しかも、透明性の優
れたフィルム或いはシートを得ることができる。例え
ば、Ｔダイ、インフレーション等の成形機を使用し、押
出温度１９０〜３５０℃、ダイス温度１９０〜３５０℃
の条件下で押出成形することによって、所望の厚さのフ
ィルムやシートを得ることができる。The acid-modified polyolefin composition of the present invention contains a heat stabilizer, a weather stabilizer, a lubricant, an antistatic agent, a nucleating agent, a filler, a pigment, a dye, a flame retardant, etc.
An additive such as an antiblocking agent may be contained in an amount of about 0.0005 to 30% by weight. By molding the thus obtained acid-modified polyolefin resin composition of the present invention according to a conventional method, a film or sheet having good adhesiveness and excellent transparency can be obtained. For example, using a molding machine such as T-die and inflation, the extrusion temperature is 190 to 350 ° C, and the die temperature is 190 to 350 ° C.
A film or sheet having a desired thickness can be obtained by extrusion molding under the conditions of.

【００２０】この様にして得られたフィルムの透明性は
透明度が５０％以上、接着強度が６００ｇ／１５ミリ幅
以上（フィルム厚みが５０〜１００μの場合）のものが
得られる。また、上記で得られたフィルム、シートを延
伸することによって透明性や機械的強度を向上させるこ
ともできる。The transparency of the thus obtained film is 50% or more and the adhesive strength is 600 g / 15 mm width or more (when the film thickness is 50 to 100 μm). Further, the transparency and mechanical strength can be improved by stretching the film or sheet obtained above.

【００２１】本発明の酸変性ポリオレフィン樹脂組成物
は、例えば、ポリオレフィン、ＥＶＯＨ、ポリアミド、
ポリエステル、ガラス、金属等を基材層として形成され
る各種積層体の接着層として好適に使用できる。基材層
を形成するポリオレフィンとしては、例えば、低密度ポ
リエチレン、線状低密度ポリエチレン、高密度ポリエチ
レン、ポリプロピレン、ポリブテン−１、またはこれら
の共重合体や組成物が挙げられる。エチレン−酢酸ビニ
ル共重合体ケン化物としてはガスバリアー性、耐油性、
水透過性等から考えてエチレン含有が２０〜６０モル
％、好ましくは２５〜５０モル％のものが挙げられる。The acid-modified polyolefin resin composition of the present invention includes, for example, polyolefin, EVOH, polyamide,
It can be suitably used as an adhesive layer for various laminated bodies formed of polyester, glass, metal or the like as a base material layer. Examples of the polyolefin forming the base material layer include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polybutene-1, or copolymers or compositions thereof. As the saponified ethylene-vinyl acetate copolymer, gas barrier properties, oil resistance,
From the viewpoint of water permeability, the ethylene content is 20 to 60 mol%, preferably 25 to 50 mol%.

【００２２】またＥＶＯＨは先に説明した様な物性のも
のが挙げられる。具体的に好ましい積層体の例として
は、例えば、ポリプロピレン又はポリエチレン層とＥＶ
ＯＨ層の接着層として、酸変性ポリプロピレン又は酸変
性ポリエチレン樹脂組成物を使用して形成される積層フ
ィルムが挙げられる。このような積層フィルムは、多層
インフレーション法、多層Ｔダイ法、多層ブロー成形
法、押出しラミネート成形法等の通常の積層体の成形法
によって製造することができる。そして、得られる積層
フィルムは、良好な接着性を有するとともに、透明性に
優れており、食品用等の包装材料等に好適に使用でき
る。Further, EVOH has the physical properties as described above. Examples of specifically preferred laminates include, for example, polypropylene or polyethylene layer and EV.
Examples of the adhesive layer of the OH layer include a laminated film formed using an acid-modified polypropylene or acid-modified polyethylene resin composition. Such a laminated film can be produced by a usual method for forming a laminated body such as a multilayer inflation method, a multilayer T-die method, a multilayer blow molding method and an extrusion laminate molding method. The obtained laminated film has good adhesiveness and excellent transparency, and can be suitably used as a packaging material for foods and the like.

【００２３】[0023]

【実施例】以下、本発明の実施例により更に詳述する
が、本発明はその要旨を超えない限り実施例に限定され
るものではない。EXAMPLES The present invention will be described in more detail below by way of examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded.

【００２４】実施例１ ポリプロピレン樹脂（三菱化成（株）製、６５００Ｊ、
ＭＦＩ＝９ｇ／１０分（２３０℃測定）、プロピレン−
エチレンランダム共重合体）８０重量部と、エラストマ
ー｛三井石油化学工業（株）製、商品名：タフマーＡ２
００９０、ＭＦＲ＝１８ｇ／１０分（１９０℃測定）、
エチレン−ブテンランダム共重合エラストマー｝２０重
量部と、無水マレイン酸１．５重量部と、２，５−ジメ
チル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−
３を０．１５重量部とを５０ｍｍφ押出機にて２１０℃
で溶融混練してペレット化を行ない、エラストマー含有
酸変性ポリオレフィン樹脂を得た。このエラストマー含
有酸変性ポリオレフィン樹脂中の無水マレイン酸のグラ
フト量は１．２重量％であった。Example 1 Polypropylene resin (6500J, manufactured by Mitsubishi Kasei Co., Ltd.)
MFI = 9 g / 10 minutes (measured at 230 ° C.), propylene-
80 parts by weight of ethylene random copolymer) and an elastomer {manufactured by Mitsui Petrochemical Industry Co., Ltd., trade name: Tufmer A2
0090, MFR = 18 g / 10 minutes (measured at 190 ° C.),
Ethylene-butene random copolymer elastomer} 20 parts by weight, maleic anhydride 1.5 parts by weight, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
0.15 parts by weight of 3 in a 50 mmφ extruder at 210 ° C
Was melt-kneaded and pelletized to obtain an elastomer-containing acid-modified polyolefin resin. The graft amount of maleic anhydride in the elastomer-containing acid-modified polyolefin resin was 1.2% by weight.

【００２５】得られたエラストマー含有酸変性ポリオレ
フィン樹脂２０重量部とポリプロピレン樹脂（商品名：
三菱ポリプロ６５００Ｊ）６０重量部、更にＥＶＯＨ樹
脂（日本合成化学工業（株）製、商品名：ソアノール３
８０３、エチレン含有量３８ｍｏｌ％、ＭＦＲ４．０ｇ
／１０分（２３０℃）２０重量部を単軸の押出機にて樹
脂に対する比エネルギーが０．６ｋＷ・ｈｒ／ｋｇ、溶
融温度２２０℃となるような条件下に溶融混合し、ペレ
ット化して酸変性ポリオレフィン樹脂組成物を得た。20 parts by weight of the obtained elastomer-containing acid-modified polyolefin resin and polypropylene resin (trade name:
60 parts by weight of Mitsubishi Polypro 6500J, EVOH resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Soarnol 3)
803, ethylene content 38 mol%, MFR 4.0 g
/ 10 minutes (230 ° C.) 20 parts by weight are melt-mixed in a single-screw extruder under conditions such that the specific energy for the resin is 0.6 kW · hr / kg and the melting temperature is 220 ° C., pelletized and acidified. A modified polyolefin resin composition was obtained.

【００２６】上記酸変性ポリオレフィン樹脂組成物を接
着層として積層フィルムを製造した。即ち、３層Ｔダイ
成形機にて上記のＥＶＯＨ樹脂を押出温度２２０℃で、
また上記ポリプロピレン樹脂を２３０℃で、酸変性ポリ
オレフィン樹脂組成物を２２０℃で、ダイス温度２４０
℃の条件で成形して、ＥＶＯＨ層／接着層／ポリプロピ
レン層（３０μ／１０μ／３０μ）の積層フィルムを得
た。得られた積層フィルムの接着強度及び透明性（透明
度）を表１に示した。A laminated film was produced using the above acid-modified polyolefin resin composition as an adhesive layer. That is, the EVOH resin was extruded at a temperature of 220 ° C. in a three-layer T-die molding machine,
In addition, the polypropylene resin at 230 ° C., the acid-modified polyolefin resin composition at 220 ° C., and the die temperature of 240
Molding was carried out under conditions of ° C to obtain a laminated film of EVOH layer / adhesive layer / polypropylene layer (30 µ / 10 µ / 30 µ). The adhesive strength and transparency (transparency) of the obtained laminated film are shown in Table 1.

【００２７】[0027]

【表１】 [Table 1]

【００２８】なお透明度については（株）村上色彩技術
研究所製の透明度測定器を用いて測定し、ＭＡＸ値で表
示した。The transparency was measured by using a transparency measuring instrument manufactured by Murakami Color Research Laboratory Co., Ltd. and expressed as a MAX value.

【００２９】実施例２ 実施例１において、ＥＶＯＨ樹脂の配合量を表１に示す
ように変えたほかは同様にして、酸変性ポリオレフィン
樹脂組成物を製造し、次いで、実施例１と同様にして積
層フィルムを得た。結果を表１に示した。Example 2 An acid-modified polyolefin resin composition was produced in the same manner as in Example 1 except that the blending amount of EVOH resin was changed as shown in Table 1, and then in the same manner as in Example 1. A laminated film was obtained. The results are shown in Table 1.

【００３０】実施例３ 実施例１において、エラストマーとして、エチレン−プ
ロピレン共重合エラストマー（日本合成ゴム（株）製、
ＥＰ０２Ｐ、ＭＦＲ＝３．２ｇ／１０分）を表１に示す
量使用したほかは同様にして酸変性ポリオレフィン樹脂
組成物を製造し、次いで、実施例１と同様にして積層フ
ィルムを得た。結果を表１に示した。Example 3 In Example 1, as the elastomer, an ethylene-propylene copolymer elastomer (manufactured by Nippon Synthetic Rubber Co., Ltd.,
EP02P, MFR = 3.2 g / 10 min) was used in the same manner as in Example 1 except that the amounts shown in Table 1 were used, and then a laminated film was obtained in the same manner as in Example 1. The results are shown in Table 1.

【００３１】実施例４ 実施例１においてエラストマーを配合しないでポリプロ
ピレン樹脂１００重量部のみに対して酸変性処理を行な
った事以外は実施例１と同様にして積層フィルムを得
た。結果を表１に示した。Example 4 A laminated film was obtained in the same manner as in Example 1 except that 100 parts by weight of the polypropylene resin was subjected to the acid modification treatment without blending the elastomer. The results are shown in Table 1.

【００３２】[0032]

【発明の効果】本発明に従い、特定条件下に酸変性ポリ
オレフィン樹脂とＥＶＯＨ樹脂とを溶融混合することに
より、ＥＶＯＨ樹脂が酸変性ポリオレフィン樹脂中にミ
クロサイズでしかも均一に分散された接着性の良好な組
成物を得ることができる。更に、該組成物を成形して得
られるフィルムまたはシートは、透明性に優れており、
包装材料などの各種積層体の接着層等として有利に使用
できる。INDUSTRIAL APPLICABILITY According to the present invention, the EVOH resin is finely and uniformly dispersed in the acid-modified polyolefin resin by melt-mixing the acid-modified polyolefin resin and the EVOH resin under a specific condition, and good adhesion is obtained. Different compositions can be obtained. Furthermore, the film or sheet obtained by molding the composition is excellent in transparency,
It can be advantageously used as an adhesive layer for various laminated bodies such as packaging materials.

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 酸変性ポリオレフィン樹脂６０〜９８重
量％とエチレン−ビニルアルコール共重合樹脂２〜４０
重量％を溶融混合して得た酸変性ポリオレフィン樹脂組
成物。1. An acid-modified polyolefin resin 60 to 98% by weight and an ethylene-vinyl alcohol copolymer resin 2 to 40.
An acid-modified polyolefin resin composition obtained by melt-mixing wt%. 【請求項２】 酸変性ポリオレフィン樹脂は、その２〜
５０重量％が酸変性ポリオレフィンエラストマーである
ことを特徴とする請求項１に記載の酸変性ポリオレフィ
ン樹脂組成物。2. The acid-modified polyolefin resin is
The acid-modified polyolefin resin composition according to claim 1, wherein 50% by weight is an acid-modified polyolefin elastomer. 【請求項３】 溶融混合は比エネルギーを０．３ｋＷ・
ｈｒ／ｋｇ以上で行なうことを特徴とする請求項１又は
請求項２に記載の組成物。3. Melt mixing has a specific energy of 0.3 kW.
The composition according to claim 1 or 2, which is performed at an hour / hr or more. 【請求項４】 酸変性ポリオレフィン樹脂、６０〜９８
重量％とエチレン−ビニルアルコール共重合樹脂、２〜
４０重量％を溶融混合して成る樹脂組成物を成形して得
た接着性フィルム又はシート。4. An acid-modified polyolefin resin, 60-98.
Wt% and ethylene-vinyl alcohol copolymer resin, 2 to
An adhesive film or sheet obtained by molding a resin composition obtained by melt mixing 40% by weight.
JP28791392A 1992-10-26 1992-10-26 Acid-modified polyolefin resin composition and adhesive film or sheet obtained using the same Expired - Fee Related JP3232317B2 (en)

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* Cited by examiner, † Cited by third party
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JP2000043040A (en) * 1998-07-27 2000-02-15 Nippon Synthetic Chem Ind Co Ltd:The Production of saponified ethylene-vinyl acetate copolymer composition pellet
JP2011178875A (en) * 2010-03-01 2011-09-15 Kyodo Printing Co Ltd Ethylene-vinyl alcohol-based polymer alloy composition, film comprising the composition, packaging material including the film, and method for producing the composition
WO2014115485A1 (en) * 2013-01-24 2014-07-31 共同印刷株式会社 Packaging bag
JP2016064610A (en) * 2014-09-26 2016-04-28 藤森工業株式会社 Laminate film and packaging bag
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