JPH04272937A - Composite polymer sheet - Google Patents
Composite polymer sheetInfo
- Publication number
- JPH04272937A JPH04272937A JP3466391A JP3466391A JPH04272937A JP H04272937 A JPH04272937 A JP H04272937A JP 3466391 A JP3466391 A JP 3466391A JP 3466391 A JP3466391 A JP 3466391A JP H04272937 A JPH04272937 A JP H04272937A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- dicyclopentadiene
- sheet
- ring
- opening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 22
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 21
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- -1 polyethylene Polymers 0.000 claims description 19
- 150000004678 hydrides Chemical class 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000306 polymethylpentene Polymers 0.000 claims description 3
- 239000011116 polymethylpentene Substances 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、複合ポリマーシートに
関するものであり、特に本発明は耐熱性、透明性、機械
的特性に優れた複合ポリマーシートに関するものである
。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite polymer sheet, and more particularly, the present invention relates to a composite polymer sheet having excellent heat resistance, transparency, and mechanical properties.
【０００２】0002
【従来の技術】ポリプロピレンのような結晶性ポリマー
に特定の石油樹脂を混合させて透明性、バリア性、耐熱
性の優れたフィルムの得られることは特開昭５８−２１
３０３７号公報、特公平１−２５５０３号公報などで知
られている。[Prior Art] It is known in JP-A-58-21 that a film with excellent transparency, barrier properties, and heat resistance can be obtained by mixing a crystalline polymer such as polypropylene with a specific petroleum resin.
This method is known from Japanese Patent Publication No. 3037 and Japanese Patent Publication No. 1-25503.
【０００３】0003
【発明が解決しようとする課題】しかし、それらのフィ
ルムには重大な欠点が存在していた。すなわち、添加樹
脂は炭化水素系のオイルとの親和性が高いためにオイル
の透過性が大きく、印刷インキがにじみ出て外観や感触
が不良になるばかりか、加熱エージングで添加樹脂がフ
ィルム表面にブリードアウトして透明性、印刷性、外観
、接着性などの特性を大幅に低下さすという欠点を有し
ていた。However, these films had significant drawbacks. In other words, since the additive resin has a high affinity with hydrocarbon oil, the oil permeability is large, and not only does the printing ink bleed out, resulting in poor appearance and feel, but also the additive resin bleeds onto the film surface during heat aging. This has the disadvantage that properties such as transparency, printability, appearance, and adhesion are significantly reduced when the film is removed.
【０００４】0004
【課題を解決するための手段】本発明は結晶性ポリマー
と、ジシクロペンタジエンの開環重合体の水素化物との
複合ポリマーからなるシートにおいて、ジシクロペンタ
ジエンの開環重合体の水素化物のガラス転移点が１００
℃以上であること特徴とする複合ポリマーシートに関す
るものである。[Means for Solving the Problems] The present invention provides a sheet comprising a composite polymer of a crystalline polymer and a hydride of a ring-opening polymer of dicyclopentadiene. Transition point is 100
The present invention relates to a composite polymer sheet characterized by having a temperature of ℃ or higher.
【０００５】本発明の結晶性ポリマーとは、結晶化しう
るポリマーのことであり、走査型熱量計（ＤＳＣ）で５
℃／分の昇温速度で加熱していったときに結晶融解に伴
なう吸熱ピークの認められるポリマーであり、その結晶
融解エネルギーΔＨｕが、３ｃａｌ ／ｇ以上、好まし
くは５ｃａｌ ／ｇ以上のものをいう。代表的なポリマ
ーとしては、ポリエステル、ポリオレフィン、ポリアミ
ド、ハロゲン含有ポリマーなどがあるが、その中でも本
発明の場合ポリオレフィンが好ましい。ポリオレフィン
とは基本的には炭素と水素とからなるポリマーであるが
、必要によっては酸素を含んだものであってもよい。代
表的な結晶性ポリオレフィンポリマーとしては、ポリエ
チレン、ポリプロピレン、ポリメチルペンテン、ポリフ
ェニレンオキサイド、ポリオキシメチレン、ポリプロピ
レンオキサイド、ポリブテン、ポリメチルブテン、ポリ
メチルヘキセン、ポリビニルシクロヘキサン、ポリビニ
ルナフタレン、ポリキシレンなどが挙げられるが、本発
明の場合、特にポリエチレン、ポリプロピレン、ポリメ
チルペンテン、ポリフェニレンオキサイド、ポリオキシ
メチレンおよびその混合体や誘導体が好ましい。[0005] The crystalline polymer of the present invention refers to a polymer that can be crystallized and has a temperature of 5.
A polymer that exhibits an endothermic peak due to crystal melting when heated at a heating rate of °C/min, and whose crystal melting energy ΔHu is 3 cal/g or more, preferably 5 cal/g or more. means. Typical polymers include polyester, polyolefin, polyamide, and halogen-containing polymer, among which polyolefin is preferred in the present invention. Polyolefin is basically a polymer consisting of carbon and hydrogen, but may contain oxygen if necessary. Typical crystalline polyolefin polymers include polyethylene, polypropylene, polymethylpentene, polyphenylene oxide, polyoxymethylene, polypropylene oxide, polybutene, polymethylbutene, polymethylhexene, polyvinylcyclohexane, polyvinylnaphthalene, polyxylene, etc. However, in the present invention, polyethylene, polypropylene, polymethylpentene, polyphenylene oxide, polyoxymethylene, and mixtures and derivatives thereof are particularly preferred.
【０００６】また、ジシクロペンタジエンの開環重合体
の水素化物とは、例えば特公昭５８−４３４１２号や特
開昭６３−２１８７２７号などでよく知られている。[0006] Hydrogenated ring-opening polymers of dicyclopentadiene are well known, for example, from Japanese Patent Publication No. 43412/1983 and Japanese Patent Application Laid-open No. 218727/1983.
【０００７】本発明の場合、重合体単独であってもよい
が、ジシクロペンタジエンとエチレンとの共重合体、例
えば特開昭６３−３１４２２０号などで知られているポ
リマーや、ジシクロペンタジエンとジエノフィルとの混
合物から４環体以上の多環ノルボルネン系化合物を得た
のち重合体にしたもの、例えば特公昭４６−１４９１０
号、特開平１−１４９７３８号、ＵＳＰ２８８３３７２
号などに示されているポリマーが特に好ましい。もちろ
んジシクロペンタジエン類は、そのメチルやエチル置換
体などのアルキル置換体や、エンド異性体、エキソ異性
体またはこれらの混合物なども含むものである。重合の
際、線状のモノオレフィン、線状の共役ジオレフィン、
シクロオレフィン等を添加して分子量や物性を調節する
ことができる。具体的にはブテン−１、ペンテン−１、
ヘキセン−１、オクテン−１、シクロペンテン、ノルボ
ルネン、１，４−ヘキサジエンなどが挙げられる。In the case of the present invention, the polymer may be used alone, but a copolymer of dicyclopentadiene and ethylene, such as the polymer known from JP-A-63-314220, or a copolymer of dicyclopentadiene and ethylene may be used. A polycyclic norbornene compound having 4 or more rings is obtained from a mixture with dienophile and then made into a polymer, for example, Japanese Patent Publication No. 46-14910
No., JP 1-149738, USP 2883372
Particularly preferred are the polymers shown in No. Of course, dicyclopentadienes also include alkyl substituted products such as methyl and ethyl substituted products, endo isomers, exo isomers, and mixtures thereof. During polymerization, linear monoolefin, linear conjugated diolefin,
Molecular weight and physical properties can be adjusted by adding cycloolefin and the like. Specifically, butene-1, pentene-1,
Examples include hexene-1, octene-1, cyclopentene, norbornene, and 1,4-hexadiene.
【０００８】本発明で用いる水素化物は二重結合のほぼ
全部を飽和させ、耐熱劣化や耐候劣化などを改良したも
のである。水素添加率は二重結合が水素添加により飽和
された率であり、その値は８０％以上、好ましくは９０
％以上、さらに好ましくは９６％以上であるのがよい。The hydride used in the present invention saturates almost all of the double bonds and has improved heat resistance deterioration and weather resistance deterioration. The hydrogenation rate is the rate at which double bonds are saturated by hydrogenation, and its value is 80% or more, preferably 90% or more.
% or more, more preferably 96% or more.
【０００９】ジシクロペンタジエン系の開環重合体の水
素化合物のガラス転移点（Ｔｇ）は１００℃以上、好ま
しくは１２０℃以上でなければならない。Ｔｇが１００
℃未満だと、複合ポリマーシートを加熱エージング、例
えば６０℃、８５ＲＨ％で１週間放置すると、添加樹脂
のブリードアウトに起因すると思われる透明性、接着性
、印刷性、外観などの悪化がおこるのみならず、炭化水
素系のオイルの透過性が大きくなり、印刷インキのにじ
み出しが生ずるなどの重大欠点につながる。The glass transition point (Tg) of the hydrogen compound of the dicyclopentadiene-based ring-opening polymer must be 100°C or higher, preferably 120°C or higher. Tg is 100
If the temperature is below ℃, if the composite polymer sheet is left for one week at 60℃ and 85RH%, the transparency, adhesion, printability, appearance, etc. will only deteriorate due to bleed-out of the added resin. Otherwise, the permeability of hydrocarbon oil increases, leading to serious drawbacks such as bleeding of printing ink.
【００１０】またジシクロペンタジエン系の開環重合体
の水素化物の分子量としては、１０００〜１０万、好ま
しくは３，５００〜３万、さらに好ましくは５，５００
〜２万の範囲のものがよい。これは、添加ポリマーのブ
リードのしやすさ、機械的特性、さらには結晶性ポリマ
ーとの相溶性などとの相関から決まるものである。[0010] The molecular weight of the hydride of the dicyclopentadiene-based ring-opening polymer is 1,000 to 100,000, preferably 3,500 to 30,000, more preferably 5,500.
A value in the range of ~20,000 is good. This is determined by the correlation with the ease of bleeding of the added polymer, mechanical properties, and compatibility with the crystalline polymer.
【００１１】結晶性ポリマー（Ａ）と、ジシクロペンタ
ジエンの開環重合体の水素化物（Ｂ）とからなる複合ポ
リマーからなるシートとは、ポリマー（Ａ）と、重合体
（Ｂ）との単なる混合・配分・添加形態（Ｉ）であって
も、ポリマー（Ａ）からなるシートと重合体（Ｂ）から
なるシートとの積層体シートの形態（ＩＩ）であっても
、さらに、形態（Ｉ）同志あるいは形態（Ｉ）と形態（
ＩＩ）との結合せた積層体シートであってもよい。本発
明の場合、ポリマー（Ａ）と重合体（Ｂ）との混合シー
ト、およびその混合シートとポリマー（Ａ）との複合シ
ートが特に好ましい。[0011] A sheet consisting of a composite polymer consisting of a crystalline polymer (A) and a hydride (B) of a ring-opening polymer of dicyclopentadiene is a sheet consisting of a simple combination of the polymer (A) and the polymer (B). Whether it is the mixing/distribution/addition form (I) or the form (II) of a laminate sheet of a sheet made of the polymer (A) and a sheet made of the polymer (B), the form (I) ) comrade or form (I) and form (
It may also be a laminate sheet combined with II). In the case of the present invention, a mixed sheet of polymer (A) and polymer (B), and a composite sheet of the mixed sheet and polymer (A) are particularly preferred.
【００１２】複合ポリマーシート中に占める重合体（Ｂ
）の割合は、０．０５〜４５重量％、好ましくは０．５
〜３０重量％、さらに好ましくは１〜２５重量％の範囲
で複合化されたものでなくてはならない。０．０５重量
％未満だと、本発明の目的である透明性や耐熱性の向上
、さらに機械的特性の向上も認められないためである。
逆に４５重量％を越えるものだと、機械的特性が大幅に
低下するのみならず、耐油性の改良もできないためであ
る。Polymer (B) occupied in the composite polymer sheet
) is 0.05 to 45% by weight, preferably 0.5
It must be composited in a range of 1 to 30% by weight, more preferably 1 to 25% by weight. This is because if it is less than 0.05% by weight, the objectives of the present invention, such as improvements in transparency and heat resistance, as well as improvements in mechanical properties, will not be observed. On the other hand, if it exceeds 45% by weight, not only will the mechanical properties be significantly reduced, but also oil resistance cannot be improved.
【００１３】次に本発明シートの製造方法について説明
する。結晶性ポリマー（Ａ）と、ジシクロペンタジエン
とエチレンとの開環共重合体の水素化物（Ｂ）とを添加
混合する。混合方法は特に限定されないが、公知のブレ
ンダーで混合しても、溶融押出機内での混合や、溶融後
のミキシングなど任意の方法をとりうる。ただ、重合体
（Ｂ）は混合前に１２０℃で８時間ほど脱水しておく必
要がある。必要によっては、相溶化剤を添加してもよい
。両ポリマーの混合溶融体を口金から吐出させ、冷却ド
ラム上で密着冷却固化させる。密着方法としては静電荷
を印加しても、プレスロールあるいはエアーで機械的に
ニップしてもよい。このようにして得られたキャストシ
ートの物理的特性は、重合体（Ｂ）の分散状態によって
大きく変わるので、重合体（Ｂ）の事前乾燥は重要であ
る。なお、必要に応じて上記キャストシートを公知の方
法で延伸配向熱処理させてもよい。Next, a method for manufacturing the sheet of the present invention will be explained. A crystalline polymer (A) and a hydride (B) of a ring-opened copolymer of dicyclopentadiene and ethylene are added and mixed. The mixing method is not particularly limited, but any method such as mixing in a known blender, mixing in a melt extruder, or mixing after melting can be used. However, it is necessary to dehydrate the polymer (B) at 120° C. for about 8 hours before mixing. If necessary, a compatibilizer may be added. A mixed melt of both polymers is discharged from the nozzle and cooled and solidified in close contact with the cooling drum. As a method of adhesion, an electrostatic charge may be applied, or mechanical nipping may be performed using a press roll or air. The physical properties of the cast sheet thus obtained vary greatly depending on the dispersion state of the polymer (B), so pre-drying the polymer (B) is important. Note that, if necessary, the cast sheet may be subjected to a stretching and orientation heat treatment by a known method.
【００１４】[0014]
【物性の測定方法】（１） 水蒸気透過率はＪＩＳ
Ｚ０２０８に従い、４０℃で測定した値であり、ｇ／
ｍ２ ・日／０．１ｍｍの単位で表わす。[Measurement method of physical properties] (1) Water vapor transmission rate is JIS
This is a value measured at 40°C in accordance with Z0208, and g/
Expressed in units of m2/day/0.1mm.
【００１５】（２） ガラス転移点（Ｔｇ）はサンプ
ル１０ｍｇを走査型熱量計ＤＳＣ−ＩＩ型（Ｐｅｒｋｉ
ｎ Ｅｌｍｅｒ社製）にセットし、窒素気流下に昇温速
度４０℃／分の速度でサーモグラフを書かせ、ベースラ
インから吸熱ピークのずれる温度と、もどる温度との算
術平均値をＴｇとする。(2) The glass transition point (Tg) was determined by measuring 10 mg of the sample using a scanning calorimeter DSC-II model (Perki
n (manufactured by Elmer), and draw a thermograph at a heating rate of 40°C/min under a nitrogen flow, and the arithmetic mean value of the temperature at which the endothermic peak deviates from the baseline and the temperature at which it returns is taken as Tg. .
【００１６】（３） 耐油性の評価は、本発明フィル
ムに厚さ４０μｍの低密度ポリエチレンフィルムをラミ
ネート後、１５×２０ｃｍ角にヒートシールで袋にし、
その中にサラダオイルを１００ｇ投入し、４０℃、８０
ＲＨ％で１ケ月放置後の油のしみ出しや、透明性の悪化
などの外観の変化のないものを良好とした。(3) Oil resistance was evaluated by laminating a 40 μm thick low-density polyethylene film on the film of the present invention, and then heat-sealing the film into a 15 x 20 cm square bag.
Pour 100g of salad oil into it and heat at 40°C to 80°C.
Those with no change in appearance such as oil exudation or deterioration of transparency after being left for one month at RH% were rated as good.
【００１７】[0017]
【発明の効果】本発明は結晶性ポリマーに特定のジシク
ロペンタジエンの開環重合体の水素化物とからなる複合
ポリマーシートにしたことにより次の様な優れた効果を
生ずるものである。すなわち、（１） 結晶性ポリマ
ーがポリオレフィンの場合、水蒸気透過率が１（ｇ／ｍ
２ 日／０．１ｍｍ）以下という優れた水蒸気バリア性
を示す。
（２） 透明性、延伸性、成形性にも優れたシートに
なる。
（３） 耐熱性にすぐれ、加熱エージングしても透明
性、接着性、印刷性などが変わらず、安定した特性を示
す。
（４） 耐油性にすぐれるため印刷性・ラミネート適
性にすぐれ、油ものの包装用途にもすぐれたガスバリア
素材となる。
（５） ヤング率が高くなり、腰が強く、シートの取
り扱い性にすぐれる。Effects of the Invention The present invention provides a composite polymer sheet comprising a crystalline polymer and a hydrogenated ring-opening polymer of dicyclopentadiene, thereby producing the following excellent effects. That is, (1) when the crystalline polymer is a polyolefin, the water vapor permeability is 1 (g/m
It exhibits excellent water vapor barrier properties of less than 2 days/0.1 mm). (2) It becomes a sheet with excellent transparency, stretchability, and moldability. (3) It has excellent heat resistance, and exhibits stable properties such as transparency, adhesion, and printability, which do not change even after heat aging. (4) Because it has excellent oil resistance, it has excellent printability and suitability for lamination, making it an excellent gas barrier material for packaging oily items. (5) The Young's modulus is high, the elasticity is strong, and the sheet is easy to handle.
【００１８】[0018]
【実施例】次に本発明を実施例によってさらに詳細に説
明する。EXAMPLES Next, the present invention will be explained in more detail by way of examples.
【００１９】実施例１
結晶性ポリマーとして住友化学（株）製の“ノーブレン
”Ｗ９００のポリプロピレンを用いた。ジシクロペンタ
ジエン系の開環重合体の水素化物としてジシクロペンタ
ジエン（４０モル％）とノルボルネン（６０モル％）と
からなる開環重合体の水素化物（ガラス転移点１３５℃
、分子量８０００）を用いた。ポリプロピレンに対し１
２０℃で４時間真空乾燥した開環重合体の水素化物を２
０重量％ブレンダーで均一混合した。Example 1 Polypropylene "Noblen" W900 manufactured by Sumitomo Chemical Co., Ltd. was used as the crystalline polymer. As a hydride of a dicyclopentadiene-based ring-opening polymer, a hydride of a ring-opening polymer consisting of dicyclopentadiene (40 mol%) and norbornene (60 mol%) (glass transition point: 135°C)
, molecular weight 8000) was used. 1 for polypropylene
The hydride of the ring-opened polymer was vacuum-dried at 20°C for 4 hours.
The mixture was uniformly mixed using a 0% by weight blender.
【００２０】かくして得られた混合原料を公知の溶融押
出機に供給し、２５５℃で溶融させ、Ｔダイ口金から４
５℃に保たれた冷却ドラム上にエアーナイフで密着冷却
固化させた。かくして得られたキャストシートを１４５
℃に保たれた熱風オーブン加熱式縦延伸装置で長手方向
に７倍延伸し、つづいて１６０℃に加熱されたテンター
内で幅方向に１０倍延伸し、さらに１６３℃を１０秒間
、幅方向に３％のリラックスをさせながら熱処理をし、
つづいて空気中でコロナ放電処理をして表面を活性化さ
せた。かくして得られたフィルムの厚さは２０μｍであ
り、特性は一覧表にして表１に示した。[0020] The mixed raw material thus obtained was fed to a known melt extruder, melted at 255°C, and extruded from the T-die nozzle to 4
The mixture was cooled and solidified in close contact with an air knife on a cooling drum kept at 5°C. The cast sheet thus obtained was 145
The film was stretched 7 times in the longitudinal direction using a hot air oven-heated longitudinal stretching device kept at 160°C, then 10 times in the width direction in a tenter heated to 160°C, and further stretched at 163°C for 10 seconds in the width direction. Heat treatment is performed while relaxing 3%,
Subsequently, the surface was activated by corona discharge treatment in air. The thickness of the film thus obtained was 20 μm, and the properties are listed in Table 1.
【００２１】この特性から明らかなように、ヤング率が
高く、熱寸法安定性にすぐれ透明性、水蒸気バリア性に
も優れたフィルムであり、経日変化の少ない取り扱い性
のよいフィルムであることが判る。As is clear from these characteristics, the film has a high Young's modulus, excellent thermal dimensional stability, transparency, and water vapor barrier properties, and is easy to handle with little change over time. I understand.
【００２２】実施例２
実施例１で用いた開環重合体の水素化物の代わりに、ジ
シクロペンタジエン（５０モル％）とエチレン（５０モ
ル％）とからなる開環重合体の水素化物（ガラス転移点
１２７℃、分子量６０００）を用いる以外は実施例１と
全く同一にして厚さ２０μｍの二軸延伸ポリプロピレン
フィルムを作った。得られたフィルムの特性を表１に示
した。Example 2 Instead of the hydride of the ring-opening polymer used in Example 1, a hydride of a ring-opening polymer (glass) consisting of dicyclopentadiene (50 mol%) and ethylene (50 mol%) was used. A biaxially stretched polypropylene film having a thickness of 20 μm was prepared in exactly the same manner as in Example 1 except that the transition temperature was 127° C. and the molecular weight was 6000. Table 1 shows the properties of the obtained film.
【００２３】実施例１の場合と同様に取り扱い性にすぐ
れた透明性のよいバリアフィルムであることがわかる。As in Example 1, it can be seen that the barrier film is easy to handle and has good transparency.
【００２４】比較例１
実施例１および２で開環重合体の水素化物を添加せず、
あとは全く実施例１と同一にして２０μｍのポリプロピ
レンフィルムを作って諸物性を比較した。Comparative Example 1 In Examples 1 and 2, no hydride of the ring-opening polymer was added,
A 20 μm polypropylene film was prepared in the same manner as in Example 1, and its physical properties were compared.
【００２５】比較例２
実施例１で用いた開環重合体の水素化物の代りに分子量
約６００、ガラス転移点７５℃のポリジシクロペンタジ
エン（“エスコレツ”５３２０：エクソン社製）を用い
る以外は実施例１と全く同様にしてフィルムを作った。Comparative Example 2 The same procedure was carried out except that polydicyclopentadiene ("Escoretsu" 5320, manufactured by Exxon) having a molecular weight of about 600 and a glass transition point of 75° C. was used instead of the hydride of the ring-opening polymer used in Example 1. A film was made exactly as in Example 1.
【００２６】[0026]
【表１】[Table 1]
【００２７】実施例３〜７
結晶性ポリマーとして表２に示したように高密度ポリエ
チレン、ポリメチルペンテン−１、ポリフェニレンオキ
サイド、ポリオキシメチレン、ナイロン６を用いた。ジ
シクロペンタジエンの開環重合体の水素化物として、ジ
シクロペンタジエン（６０モル％）とノルボルネン（４
０モル％）とからなる開環重合体の水素化物（ガラス転
移点１２６℃、分子量５８００）を用いた。該開環重合
体の水素化物はフィルム中に対して１〜２０重量％添加
した。Examples 3 to 7 As shown in Table 2, high density polyethylene, polymethylpentene-1, polyphenylene oxide, polyoxymethylene, and nylon 6 were used as crystalline polymers. As a hydrogenated ring-opening polymer of dicyclopentadiene, dicyclopentadiene (60 mol%) and norbornene (4
A hydride of a ring-opened polymer (glass transition point: 126° C., molecular weight: 5,800) was used. The hydrogenated ring-opening polymer was added in an amount of 1 to 20% by weight based on the film.
【００２８】溶融押出法によりＴダイ口金から１０℃に
保たれた冷却ドラム上に密着冷却固化させた。[0028] By the melt extrusion method, the product was cooled and solidified from a T-die die in close contact with a cooling drum kept at 10°C.
【００２９】[0029]
【表２】[Table 2]
Claims (5)
エンの開環重合体の水素化物との複合ポリマーからなる
シートにおいて、ジシクロペンタジエンの開環重合体の
水素化物のガラス転移点が１００℃以上であることを特
徴とする複合ポリマーシート。Claim 1: A sheet comprising a composite polymer of a crystalline polymer and a hydride of a ring-opening polymer of dicyclopentadiene, wherein the glass transition point of the hydride of the ring-opening polymer of dicyclopentadiene is 100°C or higher. A composite polymer sheet characterized by:
ジシクロペンタジエンとエチレンとの共重合体および／
または、ジシクロペンタジエンとジエノフィルとからな
る多環ノルボルネン系重合体であることを特徴とする請
求項１の複合ポリマーシート。2. The ring-opening polymer of dicyclopentadiene is a copolymer of dicyclopentadiene and ethylene and/or
The composite polymer sheet according to claim 1, wherein the composite polymer sheet is a polycyclic norbornene polymer comprising dicyclopentadiene and dienophile.
ィンであることを特徴とする請求項１または２の複合ポ
リマーシート。3. The composite polymer sheet according to claim 1, wherein the crystalline polymer is a crystalline polyolefin.
ン、ポリプロピレン、ポリメチルペンテン、ポリフェニ
レンオキサイド、ポリオキシメチレン、から選ばれたポ
リマーであることを特徴とする請求項３の複合ポリマー
シート。4. The composite polymer sheet according to claim 3, wherein the crystalline polyolefin is a polymer selected from polyethylene, polypropylene, polymethylpentene, polyphenylene oxide, and polyoxymethylene.
水素化物が、複合ポリマーシート中に０．０５〜４５重
量％の範囲で複合化されたことを特徴とする請求項１〜
４のいずれかに記載の複合ポリマーシート。5. A hydrogenated ring-opening polymer of dicyclopentadiene is compounded in the composite polymer sheet in an amount of 0.05 to 45% by weight.
4. The composite polymer sheet according to any one of 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3466391A JPH04272937A (en) | 1991-02-28 | 1991-02-28 | Composite polymer sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3466391A JPH04272937A (en) | 1991-02-28 | 1991-02-28 | Composite polymer sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04272937A true JPH04272937A (en) | 1992-09-29 |
Family
ID=12420679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3466391A Pending JPH04272937A (en) | 1991-02-28 | 1991-02-28 | Composite polymer sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04272937A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269213A (en) * | 1995-03-29 | 1996-10-15 | Toray Ind Inc | Heat-resistant moistureproof film |
| WO1997015622A1 (en) * | 1995-10-23 | 1997-05-01 | Mitsubishi Chemical Corporation | Crystalline olefin resin composition |
| JP2002249625A (en) * | 2001-02-27 | 2002-09-06 | Nippon Zeon Co Ltd | Polypropylene resin composition for thermoforming and polypropylene resin sheet |
| EP1160272A4 (en) * | 1998-11-18 | 2003-08-20 | Nippon Zeon Co | Heat-shrinkable film |
| EP1341053A1 (en) * | 2002-02-22 | 2003-09-03 | Xeikon International N.V. | Liquid toner composition |
| JP2004001898A (en) * | 1993-01-29 | 2004-01-08 | Nippon Zeon Co Ltd | Press-through package |
| US6924075B2 (en) | 2002-02-22 | 2005-08-02 | Xeikon International N.V. | Dry toner composition |
| US8426529B2 (en) | 2006-07-14 | 2013-04-23 | Exxonmobil Chemical Patents Inc. | Ethylene/dicyclopentadiene copolymers and functionalized derivatives thereof |
| WO2017057109A1 (en) * | 2015-09-28 | 2017-04-06 | 日本ゼオン株式会社 | Resin composition, microporous membrane, separator and secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0459218A (en) * | 1990-06-27 | 1992-02-26 | Japan Synthetic Rubber Co Ltd | Molded product of hydrogenated polymer |
-
1991
- 1991-02-28 JP JP3466391A patent/JPH04272937A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0459218A (en) * | 1990-06-27 | 1992-02-26 | Japan Synthetic Rubber Co Ltd | Molded product of hydrogenated polymer |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004001898A (en) * | 1993-01-29 | 2004-01-08 | Nippon Zeon Co Ltd | Press-through package |
| JPH08269213A (en) * | 1995-03-29 | 1996-10-15 | Toray Ind Inc | Heat-resistant moistureproof film |
| WO1997015622A1 (en) * | 1995-10-23 | 1997-05-01 | Mitsubishi Chemical Corporation | Crystalline olefin resin composition |
| EP1160272A4 (en) * | 1998-11-18 | 2003-08-20 | Nippon Zeon Co | Heat-shrinkable film |
| JP2002249625A (en) * | 2001-02-27 | 2002-09-06 | Nippon Zeon Co Ltd | Polypropylene resin composition for thermoforming and polypropylene resin sheet |
| EP1341053A1 (en) * | 2002-02-22 | 2003-09-03 | Xeikon International N.V. | Liquid toner composition |
| US6887639B2 (en) | 2002-02-22 | 2005-05-03 | Xeikon International N.V. | Liquid toner composition |
| US6924075B2 (en) | 2002-02-22 | 2005-08-02 | Xeikon International N.V. | Dry toner composition |
| US8426529B2 (en) | 2006-07-14 | 2013-04-23 | Exxonmobil Chemical Patents Inc. | Ethylene/dicyclopentadiene copolymers and functionalized derivatives thereof |
| WO2017057109A1 (en) * | 2015-09-28 | 2017-04-06 | 日本ゼオン株式会社 | Resin composition, microporous membrane, separator and secondary battery |
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