JPS6195015A - Resin composition and its molded article - Google Patents
Resin composition and its molded articleInfo
- Publication number
- JPS6195015A JPS6195015A JP21713284A JP21713284A JPS6195015A JP S6195015 A JPS6195015 A JP S6195015A JP 21713284 A JP21713284 A JP 21713284A JP 21713284 A JP21713284 A JP 21713284A JP S6195015 A JPS6195015 A JP S6195015A
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene fluoride
- resin composition
- containing polymer
- molded article
- fusion
- 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
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、透明で難燃性であると共に柔軟性の要求され
る樹脂成形品に用いられる樹脂組成物及びその樹脂組成
物の性質を利用した成形品に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention utilizes a resin composition used in resin molded products that is required to be transparent, flame retardant, and flexible, and the properties of the resin composition. This relates to molded products.
透明で難燃性の要求される樹脂成形品には、従来、塩化
ビニル樹脂（以下ＰｖＣと記す）が多く用いられてきた
。Conventionally, vinyl chloride resin (hereinafter referred to as PvC) has often been used for resin molded products that are required to be transparent and flame retardant.
更に高温で使用される樹脂成形品で、特に柔軟性が併せ
て要求されるチューブなどの成形品においては、ＰＶＣ
に代って、ポリフッ化ビニリデン（以下ＰＶｄＦ と
記す）が使用され、特に近年コンピューター、航空機等
の分野においてその使用が増加している。Furthermore, for resin molded products that are used at high temperatures, especially for molded products such as tubes that also require flexibility, PVC is used.
Instead, polyvinylidene fluoride (hereinafter referred to as PVdF) is used, and its use has been increasing particularly in the fields of computers, aircraft, etc. in recent years.
ＰＶｄ Ｆを用いた樹脂成形品についてチューブを例に
とると、ＰＶｄＦＶｄ−ブとして、ＰＶｄＦを押出機に
より溶融加工してチューブ状としたもの、ＰＶｄ Ｆに
多官能性モノマーを添加した組成物をチューブ状に成形
し、電子線加速器により照射架橋したチューブ及び、更
に照射架橋したチューブを樹脂加工して熱収縮性を付与
したチューブがある。Taking a tube as an example of a resin molded product using PVdF, PVdFVd-bu is a tube made by melt processing PVdF using an extruder, and a tube made of a composition in which a polyfunctional monomer is added to PVdF. There are tubes that are molded into a shape and cross-linked by irradiation using an electron beam accelerator, and tubes that are further cross-linked by irradiation and processed with resin to give them heat-shrinkability.
上述の如く、透明で難燃性に優れた樹脂としてＰＶｄＦ
が使用されているが、更に伸び特性に優れたものが従来
存在しなかった。例えば、ＰＶｄＦＶｄ−ブには、ＭＩ
Ｌ−Ｉ−２３０５３／８規格において、２５０“Ｃ，１
６８時間後の絶対伸びが５０％以上なければならないと
いう厳しい規格試験が課せられている。As mentioned above, PVdF is a transparent resin with excellent flame retardancy.
has been used, but there was no one with even better elongation properties. For example, the PVdFVd-bu has MI
In the L-I-23053/8 standard, 250 “C, 1
A strict standard test is imposed, requiring absolute elongation of 50% or more after 68 hours.
実際にＰＶｄＦについて上記規格試験を行なったところ
、以下の通りであった。When the above standard test was actually conducted on PVdF, the results were as follows.
ｐｖｄＦ（ＫＦポリマー１０００＋呉羽化学工業社製商
品名）１００重量部に、多官能性モノマーであるトリメ
チロールプロパントリメタクリレート５重量部を加えた
組成物をチューブ状に成形し、電子線加速器で５ Ｍｒ
ａｄ 照射して架橋させた。得られたチューブは、引
張り伸びが８５０％のものであったが、２５０℃中で１
６８時間晒した後においては、伸びが２０％となり、前
記規格値を大幅に下まわった。A composition obtained by adding 5 parts by weight of trimethylolpropane trimethacrylate, which is a polyfunctional monomer, to 100 parts by weight of pvdF (KF Polymer 1000 + trade name manufactured by Kureha Chemical Industry Co., Ltd.) was formed into a tube shape, and was heated to 5 Mr.
ad irradiation for crosslinking. The obtained tube had a tensile elongation of 850%, but the tensile elongation was 1 at 250°C.
After being exposed for 68 hours, the elongation was 20%, which was significantly below the standard value.
本発明は、透明で、上記の厳しいＭ Ｉ Ｌ規格試験に
もパスし得る高温加熱後の伸び特性に優れた樹脂組成物
及びその樹脂組成物の性質を専ら利用した成形品を提供
するもので、第１の発明の要旨とするところは、７ツ化
ビニリデンを含有する重合体に多官能性モノマーを配合
して成る組成物であって、前記フッ化ビニリデンを含有
する重合体のａｌ
融解熱量が９供→／／ 以下である樹脂組成物にあり、
第２の発明の要旨とするところは、上記樹脂組成物が成
形され、架橋されて成る成形品にある。The present invention provides a resin composition that is transparent and has excellent elongation characteristics after high-temperature heating that can pass the above-mentioned strict MIL standard test, and a molded article that exclusively utilizes the properties of the resin composition. , the gist of the first invention is a composition comprising a polyfunctional monomer blended with a polymer containing vinylidene heptadide, the al of the vinylidene fluoride-containing polymer is less than or equal to 9 →//,
The gist of the second invention resides in a molded article obtained by molding and crosslinking the resin composition.
本発明において、フッ化ビニリデンを含有する重合体と
して、ポリフッ化ビニリデン、フッ化ビニリデン共重合
体（例えば、六フッ化プロピレンーフッ化ビニリデン共
重合体）、又はこれらの重合体の混和物が使用される。In the present invention, polyvinylidene fluoride, vinylidene fluoride copolymer (e.g., propylene hexafluoride-vinylidene fluoride copolymer), or a mixture of these polymers is used as the vinylidene fluoride-containing polymer. .
多官能性モノマーとしては、例えば、トリメチロールプ
ロパントリアクリレート、トリアリルシアヌレート、ト
リアリルイソシアヌレート、トリメチロールプロパント
リアクリレートを用いることができる。As the polyfunctional monomer, for example, trimethylolpropane triacrylate, triallyl cyanurate, triallyl isocyanurate, and trimethylolpropane triacrylate can be used.
伸びが５０％以下になり、柔軟性シて劣るからである。This is because the elongation is less than 50% and the flexibility is poor.
ここに融解熱量は、示差走査熱量計（ＤＳＣ）により求
められたものである。The heat of fusion here is determined by a differential scanning calorimeter (DSC).
実施例１−４
ｐｖａＦ（ＫＦｌｏｏＯ、県別化学工業社製、商品名）
融解熱量を下げるためにフッ化ビニリデンと六フッ化プ
ロピレンの共重合体（Ｋｙｎａｒ ２８００． ペン
ウォルト社製商品名）、トリメチロールプロパン（架橋
助剤）をそれぞれ第１表に示す割合で、ロール温度２０
０℃で混練りし、その後２００°ＣでＱ、５ｍ厚のシー
トにプレス成形し、次いで、電子線を照射しく ５ Ｍ
ｒａｄ ）架橋した。Example 1-4 pvaF (KFlooO, manufactured by Kenbetsu Kagaku Kogyo Co., Ltd., trade name)
In order to lower the heat of fusion, a copolymer of vinylidene fluoride and propylene hexafluoride (Kynar 2800, a trade name manufactured by Pennwalt) and trimethylolpropane (crosslinking aid) were added in the proportions shown in Table 1, and the roll temperature was 20
The mixture was kneaded at 0°C, then press-formed at 200°C into a 5m thick sheet, and then irradiated with an electron beam.
rad) crosslinked.
尚、試験は以下の方法により行った。The test was conducted in the following manner.
（１）伸び： ＡＳＴＭ Ｄ６８８に準拠し、引張り速
度５０ＩＩＩｘ／ｍｉｎ で引張試験を行って求めた
。(1) Elongation: Determined by conducting a tensile test in accordance with ASTM D688 at a tensile rate of 50IIIx/min.
（１１）融解熱量： ＡＳＴＭ Ｄ８４１７−７５
に準拠し、ＤＳＣにより、以下の条件により求めた。(11) Heat of fusion: ASTM D8417-75
It was determined by DSC according to the following conditions.
試料的１０ ｍｌ、雰囲気Ｎ２（流量３０ ｍｌ／ｍ１
ｎ）、昇温降温速度１０℃／ｍｉｎの２回目の測定値。Sample volume: 10 ml, atmosphere N2 (flow rate: 30 ml/m1)
n), second measurement value at a temperature increase/decrease rate of 10°C/min.
実施例５〜７
ａＬｌ
融解熱が９ 幌／ Ｊ’ 以下の第２表に示すフッ化ビ
ニリデンを含有する重合体と多官能性モノマ−からなる
配合について、実施例１〜４と同様の試験を行った。そ
の結果を第２表に併記する。Examples 5 to 7 The same tests as in Examples 1 to 4 were conducted on formulations consisting of polyfunctional monomers and vinylidene fluoride-containing polymers shown in Table 2 below. went. The results are also listed in Table 2.
１） ＰＶｄＦ （２５０℃粘度： ３１Ｋｐｏｉｓ
ｅ ） 昭和電工（株〕製商品名
実施例７゜
ペンウォルト社製のフッ化ビニリデンと六フッメチロー
ルプロパントリメタクリレート５重量部を加えて成るコ
ンパウンドを、押出機により２１０°Ｃでチューブ状に
成形し、内径Ｑ、７Ｂ、外径１．３肌のチューブを得た
。その後、電子線を照射（５Ｍｒａｄ ） して、架橋
せしめた。1) PVdF (250℃ viscosity: 31Kpois
e) Product name manufactured by Showa Denko K.K. Example 7 A compound made by adding vinylidene fluoride manufactured by Pennwald Co., Ltd. and 5 parts by weight of hexafluoropropane trimethacrylate was formed into a tube shape at 210°C using an extruder. A tube with an inner diameter of Q, 7B and an outer diameter of 1.3 mm was obtained.Then, it was irradiated with an electron beam (5 Mrad) to cause crosslinking.
得られたチューブは、ゲル分率が４３％、オリジナル伸
びが３００％、２５０℃、１６８時間後の伸びａｌ
が２９０％であった。融解熱は、５．１ キー／ Ｐで
あった。The obtained tube had a gel fraction of 43%, an original elongation of 300%, and an elongation al after 168 hours at 250°C of 290%. The heat of fusion was 5.1 Key/P.
実施例８゜
実施例７において得られたチューブを２００℃に加熱し
、２倍に膨張したまま室温まで冷却して熱収縮チューブ
を作成した。Example 8 The tube obtained in Example 7 was heated to 200° C. and cooled to room temperature while being expanded to twice its original size to produce a heat-shrinkable tube.
得られた熱収縮チューブを２００℃、３分間加熱して収
縮させた後、引張り試験を行った。The obtained heat-shrinkable tube was heated at 200° C. for 3 minutes to shrink, and then a tensile test was conducted.
比較例１．２
第３表に示す組成物を実施例１〜４と同様の条件でシー
トを作成し°、同様の試験を行った。試験 、）、
結果は、第３表に併記する通りである。Comparative Example 1.2 Sheets were prepared from the compositions shown in Table 3 under the same conditions as Examples 1 to 4, and the same tests were conducted. test ,),
The results are also listed in Table 3.
第 ３ 表
１） ＰＶｄＦ （２５０℃粘度： ２５Ｋｐｏｉｓｅ
） 県側化学工業（株）裂開品名
比較例４゜
県側化学工業（株）製のＫＦポリマー１０００１００重
量部にトリメチルプロパントリメタクリレート５重量部
を加えて成るコンパウンドを実施例７と同様の条件でチ
ューブを作成した。Table 3 1) PVdF (250℃ viscosity: 25Kpoise
) Kensai Kagaku Kogyo Co., Ltd. Split product name Comparative example 4゜ A compound made by adding 5 parts by weight of trimethylpropane trimethacrylate to 100 parts by weight of KF polymer manufactured by Kensai Kagaku Kogyo Co., Ltd. was prepared under the same conditions as in Example 7. I created a tube.
フ化ビニリデンを含有する重合体を用いたものは、２５
０℃、１６８時間後の伸びは全て５０％以上であ１６８
時間後の伸びは全て５０％未満であった。Those using polymers containing vinylidene fluoride are 25
All elongations after 168 hours at 0°C were 50% or more.
All elongations after time were less than 50%.
フッ化ビニリデンを含有する重合体に多官能性Ｃ良１
モノマーを配合し、前記重合体の融解熱が９４／ｌ以下
である本発明の組成物は、透明性、難燃性及び柔軟性に
優れたもので、チューブ、テープ等の成形品に使用する
ことができる。The composition of the present invention, in which a polyfunctional C monomer is blended with a polymer containing vinylidene fluoride, and the heat of fusion of the polymer is 94/l or less, has excellent transparency, flame retardancy, and flexibility. It is an excellent material and can be used for molded products such as tubes and tapes.
Claims (5)
ノマーを配合して成る組成物であって、前記フッ化ビニ
リデンを含有する重合体の融解熱量が９ｃａｌ／ｇ以下
である樹脂組成物。(1) A resin composition comprising a polyfunctional monomer blended with a vinylidene fluoride-containing polymer, wherein the heat of fusion of the vinylidene fluoride-containing polymer is 9 cal/g or less.
化ビニリデンである特許請求の範囲第（１）項記載の樹
脂組成物。(2) The resin composition according to claim (1), wherein the vinylidene fluoride-containing polymer is polyvinylidene fluoride.
ニリデン共重合体である特許請求の範囲第（１）項記載
の樹脂組成物。(3) The resin composition according to claim (1), wherein the vinylidene fluoride-containing polymer is a vinylidene fluoride copolymer.
化ビニリデンとフッ化ビニリデン共重合体の混和物であ
る特許請求の範囲第（１）項記載の樹脂組成物。(4) The resin composition according to claim (1), wherein the vinylidene fluoride-containing polymer is a mixture of polyvinylidene fluoride and vinylidene fluoride copolymer.
ノマーを配合してなる組成物であって、前記フッ化ビニ
リデンを含有する重合体の融解熱量が９ ｃａｌ／ｇ以
下である樹脂組成物が成形され、架橋されて成ることを
特徴とする樹脂組成物成形品。(5) A resin composition comprising a vinylidene fluoride-containing polymer blended with a polyfunctional monomer, wherein the vinylidene fluoride-containing polymer has a heat of fusion of 9 cal/g or less. A resin composition molded product characterized by being formed by molding and crosslinking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21713284A JPS6195015A (en) | 1984-10-15 | 1984-10-15 | Resin composition and its molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21713284A JPS6195015A (en) | 1984-10-15 | 1984-10-15 | Resin composition and its molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6195015A true JPS6195015A (en) | 1986-05-13 |
Family
ID=16699352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21713284A Pending JPS6195015A (en) | 1984-10-15 | 1984-10-15 | Resin composition and its molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6195015A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0357329A2 (en) * | 1988-08-29 | 1990-03-07 | Minnesota Mining And Manufacturing Company | Fluorocarbon elastomers crosslinked by ionizing radiation |
| JP2008239998A (en) * | 2003-06-06 | 2008-10-09 | Arkema France | Process for grafting fluoropolymer and multilayered structure containing obtained graft polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5059317A (en) * | 1973-10-01 | 1975-05-22 | ||
| JPS5075644A (en) * | 1973-11-09 | 1975-06-20 | ||
| JPS50103551A (en) * | 1974-01-21 | 1975-08-15 |
-
1984
- 1984-10-15 JP JP21713284A patent/JPS6195015A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5059317A (en) * | 1973-10-01 | 1975-05-22 | ||
| JPS5075644A (en) * | 1973-11-09 | 1975-06-20 | ||
| JPS50103551A (en) * | 1974-01-21 | 1975-08-15 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0357329A2 (en) * | 1988-08-29 | 1990-03-07 | Minnesota Mining And Manufacturing Company | Fluorocarbon elastomers crosslinked by ionizing radiation |
| JP2008239998A (en) * | 2003-06-06 | 2008-10-09 | Arkema France | Process for grafting fluoropolymer and multilayered structure containing obtained graft polymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0203457B1 (en) | Fluoroelastomer composition and heat shrinkable articles comprising same | |
| US5109071A (en) | Fluoropolymer compositions | |
| JPH01502676A (en) | polymer composition | |
| JP2836819B2 (en) | Fluoropolymer composition | |
| US5275887A (en) | Fluoropolymer compositions | |
| US7220799B2 (en) | Radiation-modified poly (tetrafluoroethylene) resin feeds and a process for producing the same | |
| EP0073613B1 (en) | Heat-shrinkable tubes | |
| JPS6116910A (en) | Fluororesin composition crosslinkable with radiation | |
| US3265769A (en) | Biaxially oriented polypropylene film containing butyl rubber | |
| JPS6195015A (en) | Resin composition and its molded article | |
| JPH07126468A (en) | Fluororesin composition and insulated electric wire and heat-shrinkable tube made therefrom respectively | |
| JPS5911315A (en) | Compounded composition and thermally recoverable article | |
| JPS6023703B2 (en) | Method for producing heat-resistant ethylene/tetrafluoroethylene copolymer composition molded products | |
| JPS6116911A (en) | Fluororesin composition crosslinkable with radiation | |
| JPH0463849A (en) | Fluorocarbon resin composition | |
| JPS6233064B2 (en) | ||
| JPH08120145A (en) | Fluoroelastomer molded form, insulated electric wire and insulated tube | |
| JPS6215250A (en) | Fluororesin composition crosslinkable by irradiation | |
| JPH0733938A (en) | Fluororesin composition, and tube and thermally shrinkable tube produced therefrom | |
| JPH03149250A (en) | Heat-resistant resin composition | |
| JPH04122747A (en) | Flame-retardant resin composition and tube | |
| JP2993024B2 (en) | Halogen-free flame-retardant heat-shrinkable tube | |
| JPS59227437A (en) | Heat-recoverable article | |
| JPH0144249B2 (en) | ||
| JPS60227314A (en) | Thermal shrinkable tube |