JPH0218435A - Polypropylene resin composition for bonding - Google Patents
Polypropylene resin composition for bondingInfo
- Publication number
- JPH0218435A JPH0218435A JP16686988A JP16686988A JPH0218435A JP H0218435 A JPH0218435 A JP H0218435A JP 16686988 A JP16686988 A JP 16686988A JP 16686988 A JP16686988 A JP 16686988A JP H0218435 A JPH0218435 A JP H0218435A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- alkoxyalkenylsilane
- resin composition
- bonding
- graft
- 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
- -1 Polypropylene Polymers 0.000 title claims abstract description 42
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 40
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 8
- 229920000578 graft copolymer Polymers 0.000 abstract description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 229920005672 polyolefin resin Polymers 0.000 abstract description 2
- 229920005604 random copolymer Polymers 0.000 abstract description 2
- 229920001400 block copolymer Polymers 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は接着用ポリプロピレン樹脂組成物に関する。詳
しくはエチレン−酢酸ビニル共重合体鹸化物（エバール
）、ナイロン、ポリエステル等の極性基を含有するポリ
マー、或いはアルミニウム等の金属とポリプロピレン接
着するに好適な接着用ポリプロピレン樹脂組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polypropylene resin composition for adhesive use. Specifically, the present invention relates to an adhesive polypropylene resin composition suitable for adhering polypropylene to a saponified ethylene-vinyl acetate copolymer (EVAL), a polar group-containing polymer such as nylon or polyester, or a metal such as aluminum.
ポリプロピレンの特性を生かしさらにガスバリヤ−性等
のポリプロピレンが元来持たない特性を付与する目的で
他の、特に極性基を含有するポリマー、或いはアルミニ
ウム箔と多層構造にすることは広く行われている。元来
ポリプロピレンと極性基含有ポリマーは相溶性が無いた
め単に張り合わすだけでは接着せず、間に接着用の樹脂
を挟むことが行われている。この目的のためポリプロピ
レンに無水マレイン酸をグラフトした重合体が利用され
ている。In order to take advantage of the properties of polypropylene and provide properties that polypropylene does not originally have, such as gas barrier properties, it is widely practiced to form a multilayer structure with other polymers, especially those containing polar groups, or aluminum foil. Polypropylene and polar group-containing polymers are originally not compatible with each other, so they cannot be bonded by simply pasting them together; instead, an adhesive resin is sandwiched between them. For this purpose, a polymer in which maleic anhydride is grafted onto polypropylene is used.
ポリプロピレンに無水マレイン酸をグラフトした重合体
はポリプロピレンと極性基含有ポリマーとの接着性改良
に一定の効果を有するが、特にエバールとポリプロピレ
ンの接着用などには未だ不充分であり、さらに接着性の
改良された接着用の樹脂組成物の開発が望まれていた。A polymer obtained by grafting maleic anhydride onto polypropylene has a certain effect on improving the adhesion between polypropylene and a polar group-containing polymer, but it is still insufficient, especially for adhesion between EVAL and polypropylene. It has been desired to develop an improved adhesive resin composition.
本発明者らは上記課題を達成したポリプロピレンの接着
性を改良した組成物について鋭意探索し、接着性に優れ
たポリプロピレン樹脂組成物を見出し、発明を完成した
。The present inventors have earnestly searched for a composition with improved adhesiveness of polypropylene that achieves the above-mentioned problems, discovered a polypropylene resin composition with excellent adhesiveness, and completed the invention.
即ち、本発明はアルコキシアルケニルシランをグラフト
重合したポリプロピレンを含有してなる接着用ポリプロ
ピレン樹脂組成物である。そして本発明はまた。アルコ
キシアルケニルシランを立体規則性ポリプロピレンにグ
ラフトしてなるポリプロピレン共重合体と該アルコキシ
アルケニルシランを含有しない結晶性ポリプロピレンと
を溶融混合してなる接着用ポリプロピレン樹脂組成物で
ある。That is, the present invention is an adhesive polypropylene resin composition containing polypropylene graft-polymerized with alkoxyalkenylsilane. And the present invention also. This is an adhesive polypropylene resin composition prepared by melt-mixing a polypropylene copolymer obtained by grafting an alkoxyalkenylsilane onto stereoregular polypropylene and a crystalline polypropylene that does not contain the alkoxyalkenylsilane.
本発明において重要なアルコキシアルケニルシランを結
晶性プロピレンにグラフトして得たグラフト共重合体の
製造方法としては特に制限は無く種々の方法がすでに知
られている。基本的には、パーオキサイド等のラジカル
発生剤が熱分解する条件下でアルコキシアルケニルシラ
ンと結晶性のポリプロピレンを接触処理することで達成
でき、溶剤の存在下、ポリマーの溶解状態で行うか、あ
るいはヘンシェルミキサーとか押出機などで溶融混合下
に行うのが一般的であり、架橋ポリプロピレンを製造す
る方法として種々の方法が提案されている（特公昭４８
−１７１１ 、特開昭５５−４０７０１、同５４−１１
７５４９など）。また市場で架橋ポリプロピレンとして
入手することもできる。There are no particular restrictions on the method for producing the graft copolymer obtained by grafting an alkoxyalkenylsilane onto crystalline propylene, which is important in the present invention, and various methods are already known. Basically, this can be achieved by contact treatment of an alkoxyalkenylsilane and crystalline polypropylene under conditions in which a radical generator such as peroxide is thermally decomposed. It is common to perform melt mixing using a Henschel mixer or an extruder, and various methods have been proposed for producing crosslinked polypropylene (Japanese Patent Publication No. 48
-1711, JP-A-55-40701, JP-A-54-11
7549 etc.). It is also commercially available as crosslinked polypropylene.
ここでグラフト共重合体中のアルコキシアルケニルシラ
ンのグラフト量としては、特に制限はないが、共重合体
の安定性などから通常１０ｗｔ％以下とするのが好まし
い。またグラフト共重合するベースポリマーとしては、
プロピレンの単独重合体のみならず後述する他のオレフ
ィンとのランダムあるいはブロンク共重合体も利用でき
る。グラフト重合体の分子量としては特に制限はないが
、極めて高い分子量、例えば１３５°Ｃテトラリン？８
液で測定した極限粘度として１０以上にならないようす
べきである。There is no particular restriction on the amount of alkoxyalkenylsilane grafted in the graft copolymer, but it is usually preferably 10 wt % or less in view of the stability of the copolymer. In addition, as a base polymer for graft copolymerization,
Not only propylene homopolymers but also random or bronch copolymers with other olefins, which will be described later, can be used. There is no particular limit to the molecular weight of the graft polymer, but extremely high molecular weight, for example, 135°C tetralin? 8
The intrinsic viscosity measured as a liquid should not exceed 10.
一方の成分である立体規則性ポリプロピレンとしては、
プロピレンの単独重合体のみならず少量のエチレン、ブ
テン、ヘキセンなどの他のオレフィンとのランダム共重
合体、あるいはプッロク共重合体が利用できその製造法
については基本的には遷移金属化合物と有機アルミニウ
ム化合物からなる触媒でプロピレンを重合する方法であ
るが、すでに多くの方法が公知である。また市場で多種
のポリプロピレンが入手できる。One component, stereoregular polypropylene, is
In addition to propylene homopolymers, random copolymers with small amounts of other olefins such as ethylene, butene, and hexene, or proplok copolymers can be used, and their production methods basically involve transition metal compounds and organoaluminum. Many methods are already known for polymerizing propylene using a catalyst consisting of a compound. Also, many types of polypropylene are available on the market.
本発明において、アルコキシアルケニルシランをグラフ
トしたポリプロピレンとアルコキシアルケニルシラン化
合物を含有しない結晶性ポリプロピレンの混合割合とし
ては、アルコキシアルケニルシランをグラフトしたポリ
プロピレン中のアルコキシアルケニルシランの量により
異なるが、混合後アルコキシアルケニルシラン単位が全
組成物中１ｗｔ％〜１００ｗｔ ｐｐ１１程度存在する
ようにするのが一般的である。ここでアルコキシアルケ
ニルシランとしては、アルケニル基としては、ビニル、
アリル、イソプロペニル、ブテニル、アクリロイルオキ
シプロピル、などが例示でき、アルコキシとしてはメト
キシ、エトキシ、プロポキシ、ペントキシなどが例示で
き、トリアルコキシの他に、１〜２個のアルコキシ基を
アルキル基としたものでも良い。In the present invention, the mixing ratio of polypropylene grafted with alkoxyalkenylsilane and crystalline polypropylene not containing an alkoxyalkenylsilane compound varies depending on the amount of alkoxyalkenylsilane in the polypropylene grafted with alkoxyalkenylsilane, but after mixing the alkoxyalkenylsilane Generally, the silane unit is present in the total composition in an amount of about 1 wt % to 100 wt pp11. Here, as the alkoxyalkenylsilane, the alkenyl group includes vinyl,
Examples include allyl, isopropenyl, butenyl, acryloyloxypropyl, etc. Examples of alkoxy include methoxy, ethoxy, propoxy, pentoxy, etc. In addition to trialkoxy, those with 1 or 2 alkoxy groups as an alkyl group But it's okay.
本発明の組成物は極性基含有重合体とポリオレフィンの
接着用として接着層として用いる他に組成物そのものを
ポリオレフィン層として用いることができる。The composition of the present invention can be used as an adhesive layer for bonding a polar group-containing polymer and a polyolefin, and the composition itself can be used as a polyolefin layer.
〔実施例］ 以下に実施例を示しさらに本発明を説明する。〔Example] The present invention will be further explained with reference to Examples below.
実施例１
１３５°Ｃのテトラリン溶液で測定した極限粘度が１．
８０であり、ソックスレー抽出器で沸騰ｎ−ヘプクンで
６時間抽出して測定した沸騰ｎ−へブタン抽出残分の割
合が９７．５χのポリプロピレンのパウダ１００重量部
、テトラエトキシビニルシラン３重量部、ジクミルパー
オキシド０．０３重量部を加え、押出機を用い２４０’
Ｃで造粒して、トリエトキシビニルシランをグラフトし
た共重合体を得た。分析によれば、極限粘度１．４２、
トリエトキシビニルシラン含ｆｉ ２ 、４ ｗ ｔχ
であった。この共重合体１０部に対し、グラフトに用い
たポリプロピ１７１００部を混合し造粒して塗装用の樹
脂組成物を得た。Example 1 The intrinsic viscosity measured in a tetralin solution at 135°C is 1.
100 parts by weight of polypropylene powder, 3 parts by weight of tetraethoxyvinylsilane, 100 parts by weight of polypropylene powder with a boiling n-heptane extraction residue ratio of 97.5x measured by extraction with boiling n-heptane for 6 hours in a Soxhlet extractor, 3 parts by weight of tetraethoxyvinylsilane, Add 0.03 parts by weight of mil peroxide, and use an extruder for 240'
A copolymer grafted with triethoxyvinylsilane was obtained by granulation with C. According to analysis, the intrinsic viscosity is 1.42,
Contains triethoxyvinylsilane fi 2 , 4 w tχ
Met. 17,100 parts of the polypropylene used for grafting were mixed with 10 parts of this copolymer and granulated to obtain a resin composition for coating.
接着強度を測定するため、エバール（クラレ■ＩＥＰ−
Ｆ）の厚み０．２ｍｍのシートとポリプロピレンの共重
合体の厚さ０．２１のシート （上記ポリプロピレンの
共重合体で製造したもの）の間に上記接着用の組成物の
シート （厚さ０．１ｍｍ）を挟み、２２０°Ｃ，４ｇ
／ｃＪ、３ｍ１ｎで圧着した。この多層のシートの剥離
強度（インストロン引っ張り試験機を用い、ＩＩＩ ２
．５ｃｍの試験片について２３°Ｃ１１００ｍｍ／ｍｉ
ｎの引っ張り速度でのＴ型剥離強度を測定した）は２
ｋｇ ／ ｃｔＡ以上であった。To measure the adhesive strength, we used EVAL (Kuraray IEP-
A sheet of the above adhesive composition (with a thickness of 0. .1mm), 220°C, 4g
/cJ, 3m1n was crimped. The peel strength of this multilayer sheet (using an Instron tensile tester, III 2
．． 23°C 1100mm/mi for 5cm test piece
The T-peel strength was measured at a tensile speed of n) was 2
kg/ctA or more.
実施例２
グラフト共重合に際しトリエトキシビニルシランの代わ
りにメタクロイルオキシプロピルトリエトキシンランを
用い、アルコキシビニルシラン含量１．８ｗｔ％、η１
．５２であるグラフト共重合体を得た。ポリプロピレン
としてエチレンとプロピレンの共重合体（エチレン含１
４．２ｗｔχ）を用いて接着用の組成物とし接着層とし
た他は実施例１と同様にしてエバールのシートとポリプ
ロピレンのシトの接着に用いたとろＴ型ｆｆ１ｌｌ ！
強度は２ ｋｇ ／ ｃｉ以上であった。Example 2 During graft copolymerization, methacroyloxypropyltriethoxine was used instead of triethoxyvinylsilane, and the alkoxyvinylsilane content was 1.8 wt%, η1
．． A graft copolymer of No. 52 was obtained. Polypropylene is a copolymer of ethylene and propylene (ethylene containing 1
4.2wtχ) was used to form an adhesive composition and an adhesive layer, but the same procedure as in Example 1 was used to bond an EVAL sheet and a polypropylene sheet.
The strength was more than 2 kg/ci.
実施例３
エハールノシートに変え厚さ０．３１のアルミニウムの
箔を用いた他は実施例１と同様にしたところＴ型剥離強
度は１ｋｇ／ｃｄであった。Example 3 The same procedure as Example 1 was carried out except that an aluminum foil having a thickness of 0.31 mm was used instead of the Eharuno sheet, and the T-peel strength was 1 kg/cd.
本発明の接着用ポリオレフィン樹脂組成物は接着強度に
すぐれ工業的に極めて意義がある。The adhesive polyolefin resin composition of the present invention has excellent adhesive strength and is of great industrial significance.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
リプロピレンを含有してなる接着用ポリプロピレン樹脂
組成物。 ２、アルコキシアルケニルシランを立体規則性ポリプロ
ピレンにグラフトしてなるポリプロピレン共重合体と該
アルコキシアルケニルシランを含有しない結晶性ポリプ
ロピレンとを溶融混合してなる接着用ポリプロピレン樹
脂組成物。[Scope of Claims] 1. An adhesive polypropylene resin composition containing polypropylene graft-polymerized with alkoxyalkenylsilane. 2. An adhesive polypropylene resin composition prepared by melt-mixing a polypropylene copolymer obtained by grafting an alkoxyalkenylsilane onto stereoregular polypropylene and a crystalline polypropylene not containing the alkoxyalkenylsilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16686988A JPH0218435A (en) | 1988-07-06 | 1988-07-06 | Polypropylene resin composition for bonding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16686988A JPH0218435A (en) | 1988-07-06 | 1988-07-06 | Polypropylene resin composition for bonding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0218435A true JPH0218435A (en) | 1990-01-22 |
Family
ID=15839143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16686988A Pending JPH0218435A (en) | 1988-07-06 | 1988-07-06 | Polypropylene resin composition for bonding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0218435A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008512280A (en) * | 2004-09-10 | 2008-04-24 | テトラ ラバル ホールデイングス エ フイナンス ソシエテ アノニム | A polymer film, a packaging laminate including the polymer film, a packaging container formed from the packaging laminate, and a method for producing the polymer film. |
| JP2008105813A (en) * | 2006-10-26 | 2008-05-08 | Brother Ind Ltd | Printer |
-
1988
- 1988-07-06 JP JP16686988A patent/JPH0218435A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008512280A (en) * | 2004-09-10 | 2008-04-24 | テトラ ラバル ホールデイングス エ フイナンス ソシエテ アノニム | A polymer film, a packaging laminate including the polymer film, a packaging container formed from the packaging laminate, and a method for producing the polymer film. |
| JP2008105813A (en) * | 2006-10-26 | 2008-05-08 | Brother Ind Ltd | Printer |
| US8475069B2 (en) | 2006-10-26 | 2013-07-02 | Brother Kogyo Kabushiki Kaisha | Printer unit |
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