JPS626583B2 - - Google Patents
Info
- Publication number
- JPS626583B2 JPS626583B2 JP7787980A JP7787980A JPS626583B2 JP S626583 B2 JPS626583 B2 JP S626583B2 JP 7787980 A JP7787980 A JP 7787980A JP 7787980 A JP7787980 A JP 7787980A JP S626583 B2 JPS626583 B2 JP S626583B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated carboxylic
- carboxylic acid
- derivative
- film
- chemically modified
- 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.)
- Expired
Links
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 239000011342 resin composition Substances 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 14
- 229920005672 polyolefin resin Polymers 0.000 claims description 12
- 229920006257 Heat-shrinkable film Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱収縮フイルム用樹脂組成物に関し、
詳しくはポリオレフイン樹脂をベースとし、これ
に特定の表面処理を施した無機物質および化学変
性ポリオレフインを加えてなる良好な物性を有す
る熱収縮フイルム用樹脂組成物に関する。
従来から高密度ポリエチレン、低密度ポリエチ
レン等を主体とした熱収縮性フイルムが各種製品
の包装に用いられているが、機械的強度が小さい
ため、特に内容物の重量が大きかつたり、角張つ
ている場合にはフイルムが破れやすく、内容物を
破損したり損傷したりするおそれがあつた。また
このフイルムは印刷、塗装等の二次加工に不向き
であるため包装による美的効果を期待することが
できず、しかもフイルム表面が平滑であるため、
包装後の製品を段積みすると滑落するおそれがあ
つた。
そこで本発明者らは、上記従来の熱収縮性フイ
ルムの欠点を克服し、すぐれた物性の熱収縮性フ
イルムを開発すべく鋭意研究を重ねた。その結
果、特定の表面処理を施した無機物質と特殊な化
学変性ポリオレフインをポリオレフイン樹脂に加
えたものが目的とする物性を有する熱収縮性フイ
ルムの素材として好適であることを見出し、本発
明を完成するに至つた。
すなわち本発明は、(A)ポリオレフイン樹脂、(B)
不飽和カルボン酸あるいはその誘導体にて表面処
理した無機物質および(C)ポリオレフイン樹脂を液
状ゴムおよび不飽和カルボン酸あるいはその誘導
体で変性した化学変性ポリオレフインよりなる熱
収縮フイルム用樹脂組成物を提供するものであ
る。
本発明の樹脂組成物のベースである(A)成分、す
なわちポリオレフイン樹脂としては、各種のもの
が使用可能であるが、好ましくは高密度ポリエチ
レン、中密度ポリエチレン、低密度ポリエチレン
などあるいは立体規則性ポリプロピレン、アタク
チツクポリプロピレン、エチレン−プロピレン共
重合体などが用いられる。
また本発明の樹脂組成物の(B)成分である不飽和
カルボン酸あるいはその誘導体にて表面処理した
無機物質は、各種のものが考えられその製法も
様々である。ここで用いることのできる無機物質
としては、炭酸カルシウム、炭酸バリウム等の炭
酸塩、ケイ酸ナトリウム、ケイ酸アルミニウム等
のケイ酸塩、硫酸カルシウム、硫酸バリウム等の
硫酸塩、酸化チタン、酸化アルミニウム等の酸化
物さらにはタルク、クレーなどをあげることがで
きる。本発明の樹脂組成物においては、これらの
無機物質を不飽和カルボン酸あるいはその誘導体
にて表面処理したものを(B)成分として用いるわけ
であるが、ここで処理剤としての不飽和カルボン
酸は各種のものがあるが、一般的には1あるいは
2以上のエチレン性二重結合を有する炭化水素部
分と1あるいは2以上のカルボキシル基を有する
炭素数10以下の不飽和カルボン酸であり、特に、
アクリル酸、メタクリル酸、クロトン酸、ケイ皮
酸、ソルビン酸、マレイン酸、無水マレイン酸、
イタコン酸、グルタコン酸、ビニル酢酸などを単
独であるいは混合して用いることが好ましい。ま
た不飽和カルボン酸の誘導体としては、上記不飽
和カルボン酸の金属塩、アミド、イミド、エステ
ル等をあげることができる。この不飽和カルボン
酸あるいはその誘導体で前記無機物質を処理する
にあたつては、通常は15〜40℃の温度にて無機物
質と不飽和カルボン酸あるいはその誘導体とを単
に混合するだけでよい。このような処理を施した
無機物質は表面が化学的に活性な不飽和カルボン
酸あるいはその誘導体で被覆されたものとなり、
また無機物質と不飽和カルボン酸あるいはその誘
導体との間は、化学的あるいは物理的に強固に結
合しているものである。不飽和カルボン酸あるい
はその誘導体で処理した無機物質を加える代わり
に、無機物質と不飽和カルボン酸あるいはその誘
導体を別々に樹脂に加えても、無機物質表面が不
飽和カルボン酸あるいはその誘導体で被覆され
ず、不飽和カルボン酸あるいはその誘導体が単な
る滑剤として作用するにとどまり、本発明のごと
き効果を得ることはできない。
さらに本発明の樹脂組成物の(C)成分である化学
変性ポリオレフインは、組成物から形成されるフ
イルムの表面物性の向上に寄与し、フイルムの印
刷性、塗装性を良好にするものであり、ポリオレ
フイン樹脂を液状ゴムと不飽和カルボン酸(無水
物を含む)あるいはその誘導体で化学変性したも
のが好適に用いられる。ここで液状ゴムとして
は、末端ヒドロキシル化ポリブタジエンが好適で
ある。この化学変性ポリオレフインを製造するに
あたつては、ポリプロピレン等のポリオレフイ
ン、液状ゴムおよび不飽和カルボン酸またはその
誘導体をキシレン、トルエン、ヘプタン、モノク
ロルベンゼン等の溶媒中で、ベンゾイルパーオキ
サイド等のラジカル発生剤を用いて反応させれば
よい。この化学変性ポリオレフインの製法の詳細
に関しては特開昭54−124049号公報に開示されて
いる。
本発明の樹脂組成物は、基本的には前記(A)、(B)
および(C)の各成分よりなるものであるが、通常は
これら各成分を加熱溶融混合することによつて調
製される。
本発明の樹脂組成物においては、(A)、(B)、(C)各
成分の配合割合は各種条件により一義的に定める
ことはできないが、通常はポリオレフイン樹脂40
〜80重量%と不飽和カルボン酸あるいはその誘導
体にて表面処理した無機物質60〜20重量%よりな
る配合物100重量部に対して化学変性ポリオレフ
イン1〜5重量部の割合で混合するのが好まし
い。ここでポリオレフイン樹脂に対する化学変性
ポリオレフインならびに無機物質の配合割合が上
記範囲外では、組成物から得られるフイルムの強
度や印刷性等が不充分なものとなり好ましいもの
とは言い難い。
本発明の樹脂組成物においては、上記(A)、(B)、
(C)成分以外に、必要に応じて滑剤、安定剤、帯電
防止剤、顔料などの各種添加剤を加えることも有
効である。
かくして得られる本発明の樹脂組成物を素材と
して、これをインフレーシヨン成形等の成形手段
によつてフイルムに成形すれば、成形されるフイ
ルムは熱収縮性を有するため、このフイルムにて
製品を包装後、ヒートシールすれば製品に密着し
たいわゆるシユリンク包装をすることができる。
しかもこのフイルムは機械的強度が従来の熱収縮
性フイルムに比べて著しく向上しているためフイ
ルムの破れ等のトラブルが減少する。またこのフ
イルムは印刷性が良好で表面に様々な模様を施す
ことができると共に静摩擦係数が大きいため包装
した製品を段積みしても滑落のおそれがない。さ
らにこのフイルムは紙の如き風合を有するため化
粧紙として有効に利用することができる。
従つて、本発明の樹脂組成物は、食料品、書
物、文具等の包装をはじめ一般贈答用包装に好適
な熱収縮フイルムの素材として広く利用される。
次に本発明を実施例によりさらに詳しく説明す
る。
実施例1〜15、参考例1〜5および比較例1〜6
(1) 不飽和カルボン酸にて表面処理した無機物質
の製造。
所定の無機物質10Kgと予め40〜50℃に保温し
た所定の不飽和カルボン酸100gをステンレス
容器中で、温度30〜40℃にて1時間混合した
後、得られた懸濁液をメタノールで洗浄し、さ
らに80℃にて乾燥し、本発明の(B)成分である不
飽和カルボン酸にて表面処理した無機物質(以
下「処理無機物質」という。)を得た。
(2) 化学変性ポリオレフインの製造。
撹拌翼と還流装置を備えた内容積5の三口
セパラブルフラスコにポリプロピレン(メルト
インデツクス8g/10分、密度0.91g/cm3、商
品名:J700G、出光石油化学(株)製)100重量部
に対して末端ヒドロキシル化1・4−ポリブタ
ジエン(数平均分子量3000、商品名:Poly bd
R45HT、ARCO chem.Div.製)5重量部、無
水マレイン酸20重量部、ジクミルパーオキサイ
ド1.72重量部、キシレン600重量部を装入し、
油浴にて投げ込みヒーターを用いて加熱し、撹
拌下で120℃、1時間反応させ、その後140℃で
3時間反応を継続した。反応終了後、冷却し、
大過剰のアセトン中に沈澱させ、吸引撹過、さ
らに乾燥(70℃にて50時間)して白色の粉末を
得た。続いてこの粉末をソツクスレー抽出装置
に入れ、アセトンによつて16時間抽出して、未
反応のポリブタジエンおよび無水マレイン酸を
除去して本発明の(C)成分である化学変性ポリオ
レフインを得た。
(3) 樹脂組成物の製造。
高密度ポリエチレン(密度0.955g/cm3、メ
ルトインデツクス0.05、商品名:640UF、出光
石油化学(株)製)、上記(1)で得られた処理無機物
質および上記(2)で得られた化学変性ポリオレフ
インの所定量を、バンバリーミキサーで樹脂温
度150〜170℃にて10〜20分間加熱混練し、樹脂
組成物を得た。
(4) フイルムの成形。
上記(3)で得られた樹脂組成物を素材としてイ
ンフレーシヨン成形機(モダンマシンナリー
製、EW50L、ダイス径100mm)にて、樹脂温度
170〜190℃、ブローアツプ比2.2で折巾径350
mm、肉厚40μの円筒フイルムを成形した。
(5) シユリンク包装。
上記(4)で得られた円筒フイルムを切り開いて
シート状フイルムとし、このフイルムに、塩化
ビニル用インク(昭和インク(株)製、MXタイ
プ)を用いてグラビアオフセツトで図柄を印刷
し、次いでこの図柄入りのフイルムで260mm×
360mm×40mmの箱を包装し、しかる後に開口部
を220℃、1.5秒間加熱し、ヒートシールして、
さらに130℃のシユリンクトンネルを20秒間通
してシユリンク包装(収縮包装)した。
(6) フイルムならびにシユリンク包装品の物性測
定。
上記(4)で得られたフイルムの各種機械的強度
および印刷強度を次の如き方法で測定した。ま
た上記(5)で得られたシユリンク包装品の耐スリ
ツプ性を下記の如き方法で測定した。これらの
結果を表に示す。
() 引張破断強度:JIS K−6781に準拠
() エレメンドルフ引裂強度:JIS Z−1702
に準拠
() インパクト強度:JIS P−8134に準拠
() 印刷強度:フイルムに塩化ビニル用イン
ク(昭和インク(株)製、MXタイプ)をグラビ
アで図柄印刷し、48時間後にセロハンテープ
で剥離テストを行なうことにより測定した。
セロハンテープ剥離は、印刷面上に刃物で軽
く100のゴバン目を作り、これをセロハンテ
ープで剥離することにより行なつた。表中の
X/100のXはセロハンテープ剥離後に残存
するゴバン目数を示す。
() 耐スリツプ性:シユリンク包装製品
(300mm×200mm×30mm、内容物重量約1Kg)
を段積みした状態での滑落度合を調べること
により行なつた。
The present invention relates to a resin composition for heat-shrinkable film,
Specifically, the present invention relates to a resin composition for heat-shrinkable films having good physical properties, which is based on a polyolefin resin, to which an inorganic substance subjected to a specific surface treatment and a chemically modified polyolefin are added. Heat-shrinkable films made mainly of high-density polyethylene, low-density polyethylene, etc. have traditionally been used for packaging various products, but because of their low mechanical strength, they tend to be particularly heavy or angular. In some cases, the film was easily torn and there was a risk of damaging or damaging the contents. In addition, this film is not suitable for secondary processing such as printing and painting, so no aesthetic effect can be expected from packaging, and the surface of the film is smooth.
When the packaged products were stacked on top of each other, there was a risk of them falling off. Therefore, the present inventors have conducted extensive research in order to overcome the drawbacks of the conventional heat-shrinkable films and develop a heat-shrinkable film with excellent physical properties. As a result, it was discovered that a material obtained by adding an inorganic substance subjected to a specific surface treatment and a special chemically modified polyolefin to a polyolefin resin is suitable as a material for a heat-shrinkable film having the desired physical properties, and the present invention was completed. I came to the conclusion. That is, the present invention comprises (A) polyolefin resin, (B)
Provided is a resin composition for a heat-shrinkable film comprising an inorganic substance surface-treated with an unsaturated carboxylic acid or its derivative and a chemically modified polyolefin obtained by modifying (C) a polyolefin resin with a liquid rubber and an unsaturated carboxylic acid or its derivative. It is. As the component (A), which is the base of the resin composition of the present invention, that is, a polyolefin resin, various types can be used, but preferably high-density polyethylene, medium-density polyethylene, low-density polyethylene, etc. or stereoregular polypropylene are used. , atactic polypropylene, ethylene-propylene copolymer, etc. are used. In addition, various types of inorganic substances surface-treated with the unsaturated carboxylic acid or its derivative, which is the component (B) of the resin composition of the present invention, can be considered, and there are various manufacturing methods. Inorganic substances that can be used here include carbonates such as calcium carbonate and barium carbonate, silicates such as sodium silicate and aluminum silicate, sulfates such as calcium sulfate and barium sulfate, titanium oxide, aluminum oxide, etc. In addition, talc, clay, etc. can be mentioned. In the resin composition of the present invention, these inorganic substances surface-treated with an unsaturated carboxylic acid or its derivative are used as component (B), but the unsaturated carboxylic acid as the treatment agent is Although there are various types, they are generally unsaturated carboxylic acids having 10 or less carbon atoms and having a hydrocarbon moiety having one or more ethylenic double bonds and one or more carboxyl groups, and in particular,
Acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, maleic anhydride,
Itaconic acid, glutaconic acid, vinyl acetic acid and the like are preferably used alone or in combination. Further, examples of derivatives of unsaturated carboxylic acids include metal salts, amides, imides, esters, etc. of the above-mentioned unsaturated carboxylic acids. When treating the inorganic substance with the unsaturated carboxylic acid or its derivative, it is usually sufficient to simply mix the inorganic substance and the unsaturated carboxylic acid or its derivative at a temperature of 15 to 40°C. The surface of inorganic substances subjected to such treatment becomes coated with chemically active unsaturated carboxylic acids or derivatives thereof,
Further, the inorganic substance and the unsaturated carboxylic acid or its derivative are strongly bonded chemically or physically. Instead of adding an inorganic substance treated with an unsaturated carboxylic acid or its derivative, even if the inorganic substance and the unsaturated carboxylic acid or its derivative are added to the resin separately, the surface of the inorganic substance will not be coated with the unsaturated carboxylic acid or its derivative. First, the unsaturated carboxylic acid or its derivative acts only as a lubricant, and the effects of the present invention cannot be obtained. Furthermore, the chemically modified polyolefin, which is component (C) of the resin composition of the present invention, contributes to improving the surface properties of the film formed from the composition, and improves the printability and paintability of the film. A polyolefin resin chemically modified with a liquid rubber and an unsaturated carboxylic acid (including anhydride) or a derivative thereof is preferably used. As the liquid rubber, terminal hydroxylated polybutadiene is suitable. In producing this chemically modified polyolefin, radicals such as benzoyl peroxide are generated by heating a polyolefin such as polypropylene, liquid rubber, and an unsaturated carboxylic acid or its derivative in a solvent such as xylene, toluene, heptane, or monochlorobenzene. The reaction may be carried out using an agent. Details of the method for producing this chemically modified polyolefin are disclosed in JP-A-54-124049. The resin composition of the present invention basically comprises the above (A) and (B).
and (C), and is usually prepared by heating and melting and mixing these components. In the resin composition of the present invention, the blending ratio of each component (A), (B), and (C) cannot be unambiguously determined depending on various conditions, but usually polyolefin resin 40
It is preferable to mix 1 to 5 parts by weight of chemically modified polyolefin to 100 parts by weight of a compound consisting of ~80% by weight and 60 to 20% by weight of an inorganic substance surface-treated with an unsaturated carboxylic acid or its derivative. . If the blending ratio of the chemically modified polyolefin and the inorganic substance to the polyolefin resin is outside the above range, the strength, printability, etc. of the film obtained from the composition will be insufficient, and this cannot be said to be preferable. In the resin composition of the present invention, the above (A), (B),
In addition to component (C), it is also effective to add various additives such as lubricants, stabilizers, antistatic agents, and pigments as necessary. If the thus obtained resin composition of the present invention is used as a raw material and molded into a film by a molding method such as inflation molding, the molded film has heat-shrinkable properties, so that products can be manufactured using this film. After packaging, heat-sealing allows for so-called shrink packaging that tightly adheres to the product.
Moreover, this film has significantly improved mechanical strength compared to conventional heat-shrinkable films, reducing problems such as film tearing. Furthermore, this film has good printability, allowing various patterns to be applied to the surface, and has a large coefficient of static friction, so there is no risk of the packaged products slipping off when stacked on top of each other. Furthermore, since this film has a paper-like feel, it can be effectively used as decorative paper. Therefore, the resin composition of the present invention is widely used as a material for heat-shrinkable films suitable for packaging foods, books, stationery, and general gift packaging. Next, the present invention will be explained in more detail with reference to Examples. Examples 1 to 15, Reference Examples 1 to 5, and Comparative Examples 1 to 6 (1) Production of an inorganic substance surface-treated with an unsaturated carboxylic acid. 10 kg of a specified inorganic substance and 100 g of a specified unsaturated carboxylic acid kept at 40-50℃ in advance are mixed in a stainless steel container at a temperature of 30-40℃ for 1 hour, and the resulting suspension is washed with methanol. The mixture was further dried at 80° C. to obtain an inorganic material whose surface was treated with an unsaturated carboxylic acid, component (B) of the present invention (hereinafter referred to as "treated inorganic material"). (2) Production of chemically modified polyolefin. 100 parts by weight of polypropylene (melt index 8 g/10 minutes, density 0.91 g/cm 3 , trade name: J700G, manufactured by Idemitsu Petrochemical Co., Ltd.) was placed in a three-neck separable flask with an internal volume of 5 and equipped with a stirring blade and a reflux device. 1,4-polybutadiene with terminal hydroxylation (number average molecular weight 3000, product name: Poly bd
R45HT, manufactured by ARCO chem.Div.), 20 parts by weight of maleic anhydride, 1.72 parts by weight of dicumyl peroxide, and 600 parts by weight of xylene.
The mixture was heated in an oil bath using an immersion heater, and reacted with stirring at 120°C for 1 hour, and then continued at 140°C for 3 hours. After the reaction is completed, cool
The mixture was precipitated into a large excess of acetone, filtered under suction, and dried (at 70°C for 50 hours) to obtain a white powder. Subsequently, this powder was placed in a Soxhlet extractor and extracted with acetone for 16 hours to remove unreacted polybutadiene and maleic anhydride to obtain a chemically modified polyolefin, which is component (C) of the present invention. (3) Manufacture of resin composition. High-density polyethylene (density 0.955 g/cm 3 , melt index 0.05, product name: 640UF, manufactured by Idemitsu Petrochemical Co., Ltd.), the treated inorganic material obtained in (1) above and the treated inorganic substance obtained in (2) above. A predetermined amount of chemically modified polyolefin was heated and kneaded using a Banbury mixer at a resin temperature of 150 to 170°C for 10 to 20 minutes to obtain a resin composition. (4) Film forming. Using the resin composition obtained in (3) above as a material, use an inflation molding machine (Modern Machinery, EW50L, die diameter 100 mm) to
170-190℃, blow-up ratio 2.2, folding width 350
A cylindrical film with a thickness of 40 μm and a thickness of 40 μm was molded. (5) Sylink packaging. The cylindrical film obtained in (4) above is cut open to make a sheet-like film, and a pattern is printed on this film by gravure offset using vinyl chloride ink (MX type, manufactured by Showa Ink Co., Ltd.), and then This patterned film is 260mm x
Pack a 360mm x 40mm box, then heat seal the opening at 220℃ for 1.5 seconds.
Furthermore, it was passed through a shrink tunnel at 130°C for 20 seconds to be shrink wrapped. (6) Measurement of physical properties of film and Shrink packaging products. Various mechanical strengths and printing strengths of the film obtained in (4) above were measured by the following methods. In addition, the slip resistance of the shrink-wrapped product obtained in (5) above was measured by the following method. These results are shown in the table. () Tensile breaking strength: Based on JIS K-6781 () Elmendorf tearing strength: JIS Z-1702
() Impact strength: Compliant with JIS P-8134 () Printing strength: Print a pattern on the film with gravure ink for vinyl chloride (MX type, manufactured by Showa Ink Co., Ltd.), and perform a peeling test with cellophane tape after 48 hours. It was measured by performing the following.
Peeling off the cellophane tape was performed by making 100 goblets lightly with a knife on the printed surface and peeling them off with cellophane tape. In the table, X in X/100 indicates the number of goblets remaining after peeling off the cellophane tape. () Slip resistance: Shrink packaging product (300mm x 200mm x 30mm, content weight approximately 1Kg)
This was done by examining the degree of slippage in a stacked state.
【表】【table】
Claims (1)
あるいはその誘導体にて表面処理した無機物質お
よび(C)ポリオレフイン樹脂を液状ゴムおよび不飽
和カルボン酸あるいはその誘導体で化学変性した
化学変性ポリオレフインよりなる熱収縮フイルム
用樹脂組成物。 2 (A)ポリオレフイン樹脂40〜80重量%と(B)不飽
和カルボン酸あるいはその誘導体にて表面処理し
た無機物質60〜20重量%よりなる配合物100重量
部に対して(C)ポリオレフイン樹脂を液状ゴムおよ
び不飽和カルボン酸あるいはその誘導体で化学変
性した化学変性ポリオレフイン1〜5重量部を混
合してなる特許請求の範囲第1項記載の組成物。[Claims] 1 (A) polyolefin resin, (B) an inorganic substance surface-treated with unsaturated carboxylic acid or its derivative, and (C) polyolefin resin chemically modified with liquid rubber and unsaturated carboxylic acid or its derivative. A resin composition for heat-shrinkable films made of chemically modified polyolefin. 2. Add (C) polyolefin resin to 100 parts by weight of a blend consisting of (A) 40-80% by weight of polyolefin resin and (B) 60-20% by weight of an inorganic substance surface-treated with unsaturated carboxylic acid or its derivative. 2. The composition according to claim 1, comprising a mixture of liquid rubber and 1 to 5 parts by weight of a chemically modified polyolefin chemically modified with an unsaturated carboxylic acid or a derivative thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7787980A JPS573841A (en) | 1980-06-11 | 1980-06-11 | Resin composition for heat-shrinkable film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7787980A JPS573841A (en) | 1980-06-11 | 1980-06-11 | Resin composition for heat-shrinkable film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS573841A JPS573841A (en) | 1982-01-09 |
JPS626583B2 true JPS626583B2 (en) | 1987-02-12 |
Family
ID=13646348
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7787980A Granted JPS573841A (en) | 1980-06-11 | 1980-06-11 | Resin composition for heat-shrinkable film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS573841A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0682168U (en) * | 1993-05-12 | 1994-11-25 | 有限会社アサヒ化成 | Clip for hose support |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60163950A (en) * | 1984-02-07 | 1985-08-26 | Asahi Chem Ind Co Ltd | Polypropylene resin composition |
JPS61221263A (en) * | 1985-03-27 | 1986-10-01 | Fujikura Ltd | Highly filled resin composition |
JPS62177040A (en) * | 1986-01-31 | 1987-08-03 | Nippon Telegr & Teleph Corp <Ntt> | Acid-resistant flame-retardant material |
JP4714432B2 (en) * | 2004-07-09 | 2011-06-29 | スリーエム イノベイティブ プロパティズ カンパニー | Thermally conductive sheet |
JP4869584B2 (en) | 2004-12-03 | 2012-02-08 | スリーエム イノベイティブ プロパティズ カンパニー | Thermally conductive sheet and method for producing the same |
US8137773B2 (en) | 2005-11-30 | 2012-03-20 | Mitsubishi Plastics, Inc. | Polyolefin series heat-shrinkable film, molded product and heat-shrinkable laminated label employing the film, and container |
-
1980
- 1980-06-11 JP JP7787980A patent/JPS573841A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0682168U (en) * | 1993-05-12 | 1994-11-25 | 有限会社アサヒ化成 | Clip for hose support |
Also Published As
Publication number | Publication date |
---|---|
JPS573841A (en) | 1982-01-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4302554A (en) | Film for heat sealing and process of heat sealing | |
US4288497A (en) | Silicone-coated article and process for production thereof | |
JPH078532B2 (en) | Drawing method for resin sheet | |
JPS626583B2 (en) | ||
JP3677928B2 (en) | Propylene resin thermoforming sheet manufacturing method | |
US6656995B2 (en) | Process for producing olefin polymer composites having improved melt strength | |
JP2009126924A (en) | Heat-sealing adhesive and heat-sealing lid material coated with the adhesive | |
US20020136843A1 (en) | High temperature and high humidity release coating for polymer film | |
JP4279686B2 (en) | Filler composite | |
JPS58222133A (en) | Propylene polymer composition having improved coatability | |
JPS626584B2 (en) | ||
DE19752657A1 (en) | Self-adhesive packaging film, especially for food | |
JPS629135B2 (en) | ||
JP2001294677A (en) | Film for heat-sealing | |
JPH0345744B2 (en) | ||
JPH0318659B2 (en) | ||
JP3173740B2 (en) | Saponified ethylene-vinyl acetate copolymer solution and use thereof | |
JP3193964B2 (en) | Adhesive laminated film | |
JP3714649B2 (en) | Resin composition for film | |
JPH01123844A (en) | Heat-resistant container | |
JPH05154445A (en) | Production of heat sealable cap material | |
US3442836A (en) | Vinylidene chloride copolymer coating composition for water-sensitive organic polymer film | |
JPH0367111B2 (en) | ||
JP3457050B2 (en) | Saponified ethylene-vinyl acetate copolymer solution and its use | |
WO2004031480A1 (en) | Recyclable moistureproof packaging paper |