JPH02163132A - Molding method of vinylidene fluoride polymer composition - Google Patents

Molding method of vinylidene fluoride polymer composition

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Publication number
JPH02163132A
JPH02163132A JP31723988A JP31723988A JPH02163132A JP H02163132 A JPH02163132 A JP H02163132A JP 31723988 A JP31723988 A JP 31723988A JP 31723988 A JP31723988 A JP 31723988A JP H02163132 A JPH02163132 A JP H02163132A
Authority
JP
Japan
Prior art keywords
vinylidene fluoride
fluoride polymer
hydroxide
molding
glass fiber
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
Application number
JP31723988A
Other languages
Japanese (ja)
Inventor
Atsuto Kobayashi
小林 淳人
Keizo Abe
阿部 桂三
Takahiro Ozu
小津 孝弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Petrochemical Co Ltd
Original Assignee
Mitsubishi Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Petrochemical Co Ltd filed Critical Mitsubishi Petrochemical Co Ltd
Priority to JP31723988A priority Critical patent/JPH02163132A/en
Publication of JPH02163132A publication Critical patent/JPH02163132A/en
Pending legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To obtain a molded article with a glass fiber of low cost and without generation of a hydrogen fluoride gas having deadly poison by molding a composition composed of vinylidene fluoride polymer, glass fiber and a specific metallic compound such as zinc oxide at specific temperature. CONSTITUTION:100 pts.wt. in total of 50-99wt.% vinylidene fluoride polymer obtained by emulsion polymerization and 50-1wt.% glass fiber is mixed with 0.05-30 pts.wt. at least one metallic compound (preferably zinc oxide or aluminum oxide) selected from a group composed of zinc oxide, aluminum oxide, tin oxide, zinc hydroxide, calcium hydroxide, aluminum hydroxide and magnesium hydroxide and the resultant composition is molded at 180-250 deg.C.

Description

【発明の詳細な説明】 [産業上の利用分野J 本発明は、フッ化ビニリデン重合体組成物の成形法に関
し、特にガラス繊維で強化されたフッ化ビニリデン重合
体の分解を抑制したフッ化ビニリデン重合体組成物の成
形法に関するものである。
Detailed Description of the Invention [Industrial Field of Application J] The present invention relates to a method for molding vinylidene fluoride polymer compositions, and particularly relates to a method for molding vinylidene fluoride polymer compositions, in particular vinylidene fluoride polymers that suppress the decomposition of vinylidene fluoride polymers reinforced with glass fibers. The present invention relates to a method for molding a polymer composition.

[従来の技術1 一般に、使用目的に適合した樹脂性能にすることを目的
として、その樹脂が不足する物理的性質を補うために、
各種無機充填剤を配合することが、この種技術において
普通に行なわれていることであり、特に、アスペクト比
の大きい充填剤、中でもガラス繊維は、その配合によっ
て線膨張率の減少や剛性、強度の向上環の効果が大きい
ため、好んで樹脂に配合されている。
[Prior art 1] In general, in order to make the resin performance suitable for the purpose of use, in order to compensate for the physical properties that the resin lacks,
It is common practice in this type of technology to blend various inorganic fillers.In particular, fillers with a large aspect ratio, especially glass fiber, can reduce linear expansion coefficient, increase rigidity, and improve strength. Because of its great ring-enhancing effect, it is preferred to be added to resins.

一方、フッ化ビニリデン重合体は、簡便に成形でき、し
かも、耐候性や耐薬品性などの性質が優れているので、
各種材料として種々の分野にて使用されている。そこで
、このフッ化ビニリデン重合体に無機充填剤を配合して
強化し、より広範囲に、かつ−層高度に各種分野で使用
することが試みられている。
On the other hand, vinylidene fluoride polymers can be easily molded and have excellent properties such as weather resistance and chemical resistance.
It is used as various materials in various fields. Therefore, attempts have been made to strengthen this vinylidene fluoride polymer by blending it with an inorganic filler so that it can be used more widely and at a higher level in various fields.

[発明が解決しようとする課題] しかしながら、これらの無機充填剤のうち、安価で、か
つ、効果の大きいガラス繊維は、これをフッ化ビリデン
重合体に配合して成形加工したときに、フッ化ビニリデ
ン重合体の熱分解を促進させて、猛毒のフッ化水素ガス
を爆発的に大量に発生させる作用があり、安全性の面か
ら問題があった。
[Problems to be Solved by the Invention] However, among these inorganic fillers, glass fiber, which is inexpensive and has a large effect, is fluorinated when it is blended with a pyridene fluoride polymer and molded. It has the effect of accelerating the thermal decomposition of vinylidene polymers and explosively generating large amounts of highly poisonous hydrogen fluoride gas, which poses a safety problem.

したがって、フッ化ビニリデン重合体に配合されるガラ
ス繊維としては、特殊な組成のガラス繊維(特開昭52
−108450号公報参照)を用いることも提案されて
いるが、通常は、ガラス繊維の代りにカーボン繊維が用
いられ、そのために得られる製品は高価なものとなり、
その用途が限定されていた。
Therefore, as the glass fiber blended into vinylidene fluoride polymer, glass fiber with a special composition (Japanese Unexamined Patent Publication No. 52
Although it has been proposed to use carbon fiber (see Japanese Patent No. 108450), carbon fiber is usually used instead of glass fiber, and the resulting product is therefore expensive.
Its use was limited.

[課題を解決するための手段1 本発明者等は5通常のガラス繊維を配合した場合でもフ
ッ化ビニリデン重合体の熱分解が抑制されることを目的
として鋭意研究を重ねた結果、特定の重合方法で得られ
たフッ化ビニリデン重合体を用い、かつ、特定の金属化
合物を配合して、特定な温度範囲で成形することによっ
て、この目的を達成することができることを見出し、本
発明を完成するに至った。
[Means for Solving the Problems 1] As a result of extensive research aimed at suppressing the thermal decomposition of vinylidene fluoride polymers even when blended with ordinary glass fibers, the present inventors found that They discovered that this objective could be achieved by using a vinylidene fluoride polymer obtained by a method, blending a specific metal compound, and molding it at a specific temperature range, and completed the present invention. reached.

すなわち、本発明は、エマルジョン重合で得られたフッ
化ビニリデン重合体50〜99重量%及びガラス繊維5
0〜1重量%の合計量100重量部に対して、酸化亜鉛
、酸化アルミニウム、酸化錫、水酸化亜鉛、水酸化カル
シウム、水酸化アルミニウム及び水酸化マグネシウムか
らなる群より選ばれた少なくとも一種の金属化合物を0
.05〜30重量部配合してなる組成物を180〜25
8℃で成形することを特徴とするフッ化ビニリデン重合
体組成物の成形法である。
That is, the present invention uses 50 to 99% by weight of vinylidene fluoride polymer obtained by emulsion polymerization and 5% by weight of glass fibers.
At least one metal selected from the group consisting of zinc oxide, aluminum oxide, tin oxide, zinc hydroxide, calcium hydroxide, aluminum hydroxide, and magnesium hydroxide, relative to 100 parts by weight of the total amount of 0 to 1% by weight. Compound 0
.. A composition containing 05 to 30 parts by weight is 180 to 25 parts by weight.
This is a method for molding a vinylidene fluoride polymer composition, which is characterized by molding at 8°C.

[発明の詳細な説明] フッ化ビニリデン小人 本発明の成形法において、成形される組成物に使用され
るフッ化ビニリデン重合体は、エマルジョン重合によっ
て得られた、フッ化ビニリデンの単独重合体又はフッ化
ビニリデンを60重量%以上含有する共重合体である。
[Detailed Description of the Invention] Vinylidene Fluoride Dwarf In the molding method of the present invention, the vinylidene fluoride polymer used in the composition to be molded is a vinylidene fluoride homopolymer or a vinylidene fluoride homopolymer obtained by emulsion polymerization. It is a copolymer containing 60% by weight or more of vinylidene fluoride.

このような共重合体の製造においてフッ化ビニリデンと
の共重合に用いられる共単量体としては、例えばテトラ
フルオロエチレン、ヘキサフルオロプロピレン、(メタ
)アクリル酸エステル、エチレンなどがある。
Examples of the comonomer used for copolymerization with vinylidene fluoride in the production of such a copolymer include tetrafluoroethylene, hexafluoropropylene, (meth)acrylic acid ester, and ethylene.

フッ化ビニリデン重合体を製造する方法としては、エマ
ルジョン重合法以外にサスペンション重合法もあるが、
サスペンション重合法で得られたフッ化ビニリデン重合
体は熱分解を抑制する効果が奏されない。
In addition to emulsion polymerization, there is also suspension polymerization as a method for producing vinylidene fluoride polymer.
Vinylidene fluoride polymers obtained by suspension polymerization do not have the effect of suppressing thermal decomposition.

更に、これらフッ化ビニリデン重合体の中では、ポリマ
ー構造のへッドーテイル不規則性(ボッマー主鎖の水素
原子とフッ素原子の結合の繰返しの乱れ: NMRで測
定)が4.0〜15.0%、好ましくは4.0〜lO,
0%のものは、熱分解の抑制効果が大きいので好ましい
。一般にエマルジョン重合のフッ化ビニリデン重合体は
へラド−ディル不規則性がサスペンション重合のものに
比べて高い。
Furthermore, among these vinylidene fluoride polymers, headtail irregularity (disorder of repeated bonds between hydrogen atoms and fluorine atoms in the Bommer main chain: measured by NMR) of the polymer structure is 4.0 to 15.0%. , preferably 4.0 to lO,
0% is preferable because it has a large effect of suppressing thermal decomposition. In general, vinylidene fluoride polymers produced by emulsion polymerization have higher Herradyl irregularity than those produced by suspension polymerization.

及之ス罐雅 本発明のフッ化ビニリデン重合体組成物の成形法におい
て使用するガラス繊維としては、通常重版されているも
のの中から適宜選んで用いることができ、例えばEガラ
スが好適であるが、一般に直径が5〜25μm、好まし
くは10〜20μm、長さが口、5〜10mm、好まし
くは1〜7mmのものである。また、前記特開昭52−
108450号公報に提案される酸化&lll素成分が
6%以下のガラス繊維も、フッ化ビニリデン重合体の熱
分解を起こし難いので勿論好ましいものである。
The glass fiber used in the method for molding the vinylidene fluoride polymer composition of the present invention can be appropriately selected from those that are usually reprinted, and for example, E glass is preferred. , generally having a diameter of 5 to 25 μm, preferably 10 to 20 μm, and a length of 5 to 10 mm, preferably 1 to 7 mm. In addition, the above-mentioned Unexamined Patent Publication No. 52-
The glass fibers proposed in Japanese Patent No. 108450, which contain 6% or less of the oxidized &llllium component, are of course preferable because they are less likely to cause thermal decomposition of the vinylidene fluoride polymer.

亀匡止介進 本発明のフ・ン化ビニリデン重合体組成物の成形法にお
いて用いられる金属化合物としては、酸化亜鉛、酸化ア
ルミニウム、酸化錫、水酸化亜鉛、水酸化カルシウム、
水酸化アルミニウム及び水酸化マグネシウムからなる群
より選ばれた少なくとも一種の化合物がある。これらの
中でも、特に酸化亜鉛、酸化アルミニウムは射出成形時
に成形体表面の荒れが発生し難いので好ましい添加物で
ある。これら金属化合物は通常粉末状のものが使用され
る。
Metal compounds used in the method of molding the vinylidene fluoride polymer composition of the present invention include zinc oxide, aluminum oxide, tin oxide, zinc hydroxide, calcium hydroxide,
There is at least one compound selected from the group consisting of aluminum hydroxide and magnesium hydroxide. Among these, zinc oxide and aluminum oxide are particularly preferable additives because they are less likely to cause roughness on the surface of the molded product during injection molding. These metal compounds are usually used in powder form.

配イび1合 これら成分の配合割合は、フッ化ビニリデン重合体を5
0〜99重遣%、好ましくは60〜80重雀%及びガラ
ス繊維を50〜1重量%、好ましくは40〜20重量%
の割合で配合し、その合計量100重量部に対して、上
記金属化合物を0.05〜30重量部、好ましくは0.
07〜IO重量部、特に好ましくは0.08〜5重量部
の範囲で配合する。
The blending ratio of these components is 5% vinylidene fluoride polymer
0 to 99% by weight, preferably 60 to 80% by weight, and 50 to 1% by weight, preferably 40 to 20% by weight of glass fiber.
0.05 to 30 parts by weight, preferably 0.05 to 30 parts by weight, of the metal compound to 100 parts by weight of the total amount.
0.07 to IO parts by weight, particularly preferably 0.08 to 5 parts by weight.

前記フッ化ビニリデン重合体とガラス繊維の配合量が上
記範囲以外のものは、剛性強度の向上効果が生じ難いの
で好ましくない。また、上記金属化合物が上記範囲より
少な過ぎるとフッ化ビニリデン重合体の熱分解抑制の効
果が得られず、上記範囲より多過ぎるとフッ化ビニリデ
ン重合体組成物の機械的強度や耐薬品性に悪影響を及ぼ
すので好ましくない。
If the blending amount of the vinylidene fluoride polymer and glass fiber is outside the above range, it is not preferable because the effect of improving rigidity and strength is unlikely to occur. In addition, if the amount of the metal compound is too less than the above range, the effect of suppressing thermal decomposition of the vinylidene fluoride polymer will not be obtained, and if it is too much than the above range, the mechanical strength and chemical resistance of the vinylidene fluoride polymer composition will be affected. This is not desirable as it has a negative effect.

i匹皿辺厘分 本発明においては、これら必須成分の外に、必要に応じ
て他の樹脂、充填剤、着色剤などを本発明の効果を著し
く損なわない範囲で適宜配合することができる。
In the present invention, in addition to these essential components, other resins, fillers, coloring agents, etc. may be appropriately blended as needed within a range that does not significantly impair the effects of the present invention.

このような諸成分からなる組成物は、予め、通常の混合
機又は混線機で混合、造粒などの工程を付加してもよく
、又、多成分を直接に成形機に投入して成形してもよい
し、或いは、予め特定の成分を高濃度に混ぜたマスター
バッチとしてあき、成形時に所定の濃度になるよう希釈
しながら成形することもできる。
A composition consisting of such various components may be prepared by adding processes such as mixing and granulation using an ordinary mixer or mixer, or may be molded by directly feeding the multiple components into a molding machine. Alternatively, it is also possible to prepare a master batch in which specific components are mixed at a high concentration in advance, and then to mold the material while diluting it to a predetermined concentration during molding.

成形 本発明のフッ化ビニリデン重合体組成物の成形法におい
て行なわれる成形は、通常の押出成形、射出成形、圧縮
成形などで行なうが、その際。
Molding In the molding method of the vinylidene fluoride polymer composition of the present invention, the molding is carried out by conventional extrusion molding, injection molding, compression molding, etc.

180〜258℃、好ましくは190〜230℃の温度
条件下で行なうことが必要である。成形温度が上記温度
範囲よりも低温過ぎると成形し難かったり、生産性が下
る。一方、上記温度範囲よりも高過ぎるとフッ化ビニリ
デン重合体の熱分解抑制効果が奏されない。
It is necessary to conduct the reaction at a temperature of 180 to 258°C, preferably 190 to 230°C. If the molding temperature is lower than the above temperature range, molding may be difficult or productivity will decrease. On the other hand, if the temperature is too high than the above range, the effect of suppressing thermal decomposition of the vinylidene fluoride polymer will not be achieved.

[実施例J 本発明のフッ化ビニリデン重合体組成物の成形法につい
て、以下に実施例を挙げて更に説明するが、本発明はこ
れに限定されるものではない。
[Example J The method for molding the vinylidene fluoride polymer composition of the present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

実施例及び比較例の組成物で用いられた各成分は以下の
ものである。
The components used in the compositions of Examples and Comparative Examples are as follows.

fat フッ化ビニリデン重合体 (a−11米国Pennwalt社製「にynar72
0」。
fat Vinylidene fluoride polymer (a-11 manufactured by Pennwalt in the United States "Nynar72")
0”.

エマルジョン重合体、ヘッドーテイル不規則性4.6% fa−21呉羽化学社製[にFlooOJ :サスベン
ジョン重合体、ヘッドーテイル不規則性3.7% (blガラス繊維 旭ファイバーグラス社製「グラスロン チョツプドストランド」 (cl金属化合物 tc−11酸化亜鉛 (c−2)酸化アルミニウム 1c−3)酸化錫 (c−41水酸化曲鉛 (c−51水酸化カルシウム (c−61水酸化アルミニウム 1c−7)水酸化マグネシウム また、名神の測定は以下の方法による。
Emulsion polymer, head-to-tail irregularity 4.6% FA-21 manufactured by Kureha Chemical Co., Ltd. [FlooOJ: Suspension polymer, head-to-tail irregularity 3.7% (bl glass fiber manufactured by Asahi Fiberglass Co., Ltd. "Glass Ron Chopped") (Cl metal compound TC-11 Zinc oxide (C-2) Aluminum oxide 1C-3) Tin oxide (C-41 Bent hydroxide (C-51 Calcium hydroxide (C-61 Aluminum hydroxide 1C-7) Magnesium hydroxide and Meishin are measured by the following method.

+f)ヘッドーテイル不規則性 測定法 :”C−NMR法 測定機器9日本電子■製r FX−200型」測定溶剤
: Ethylene carbonate/C5Ds
(3/11測定温度=130℃ 測定濃度:15重量% (2)熱分解温度 測定機器 :理学電機■製[サーモフレック ス8800型 TG−DTA測定機] サンプル量 : 10mg 雰囲気   :空気中 昇温速度  、lO℃/分 測定温度領域、0〜500℃ 評価法   :サンプルが1重量%減少したときの温度
を比較した。
+f) Head-tail irregularity measurement method: “C-NMR method measurement equipment 9 JEOL Ltd. r FX-200 type” Measurement solvent: Ethylene carbonate/C5Ds
(3/11 measurement temperature = 130℃ Measurement concentration: 15% by weight (2) Pyrolysis temperature measurement device: Rigaku Denki [Thermoflex 8800 model TG-DTA measurement device] Sample amount: 10mg Atmosphere: Temperature increase rate in air , lO<0>C/min measurement temperature range, 0 to 500<0>C Evaluation method: The temperature was compared when the sample was reduced by 1% by weight.

(3)衝撃強度 アイゾツト衝撃強度 JIS K7110に準拠。(3) Impact strength Izotsu impact strength Compliant with JIS K7110.

(ノツチ付) 実施例1−1o及び比較例1〜5 第1表に示す配合の組成物を、東洋精機■製「ラボブラ
ストミルR60型」を用いて樹脂温度230℃、60r
pmにて60分間溶融混練して得た。
(With a notch) Example 1-1o and Comparative Examples 1 to 5 The compositions shown in Table 1 were heated at a resin temperature of 230°C and 60 rpm using a "Labo Blast Mill R60" manufactured by Toyo Seiki ■.
It was obtained by melt-kneading at pm for 60 minutes.

得られた混練物を200℃の温度で圧縮成形して、厚さ
2+on+のシートを製造し、このものの熱分解温度及
び衝撃強度を測定した。
The obtained kneaded product was compression molded at a temperature of 200° C. to produce a sheet with a thickness of 2+on+, and the thermal decomposition temperature and impact strength of this sheet were measured.

結果は第1表に示す。The results are shown in Table 1.

[発明の効果] 本発明のフッ化ビニリデン重合体組成物の成形法は、フ
ッ化ビニリデン重合体に通常のガラス繊維を配合して成
形加工しても、ガラス繊維がフッ化ビニリデン重合体の
熱分解を促進することが無いので、猛毒のフッ化水素ガ
スが爆発的に発生する危険性がなく、安全に成形するこ
とができる。
[Effects of the Invention] The method for molding the vinylidene fluoride polymer composition of the present invention is such that even if the vinylidene fluoride polymer is blended with ordinary glass fibers and processed, the glass fibers do not absorb the heat of the vinylidene fluoride polymer. Since it does not accelerate decomposition, there is no risk of explosively generating highly toxic hydrogen fluoride gas, and it can be molded safely.

しかも、安価な通常のガラス繊維をフッ化ビニリデン重
合体に配合することができるので、カーボン繊維を配合
する従来の方法に比べると、経済的に極めて有利な方法
である。
Furthermore, since inexpensive ordinary glass fibers can be blended with the vinylidene fluoride polymer, this method is economically extremely advantageous compared to the conventional method of blending carbon fibers.

Claims (1)

【特許請求の範囲】[Claims] (1)エマルジョン重合で得られたフッ化ビニリデン重
合体50〜99重量%及びガラス繊維50〜1重量%の
合計量100重量部に対して、酸化亜鉛、酸化アルミニ
ウム、酸化錫、水酸化亜鉛、水酸化カルシウム、水酸化
アルミニウム及び水酸化マグネシウムからなる群より選
ばれた少なくとも一種の金属化合物を0.05〜30重
量部配合してなる組成物を180〜258℃で成形する
ことを特徴とするフッ化ビニリデン重合体組成物の成形
法。
(1) Zinc oxide, aluminum oxide, tin oxide, zinc hydroxide, A composition comprising 0.05 to 30 parts by weight of at least one metal compound selected from the group consisting of calcium hydroxide, aluminum hydroxide, and magnesium hydroxide is molded at 180 to 258°C. A method for molding vinylidene fluoride polymer compositions.
JP31723988A 1988-12-15 1988-12-15 Molding method of vinylidene fluoride polymer composition Pending JPH02163132A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP31723988A JPH02163132A (en) 1988-12-15 1988-12-15 Molding method of vinylidene fluoride polymer composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP31723988A JPH02163132A (en) 1988-12-15 1988-12-15 Molding method of vinylidene fluoride polymer composition

Publications (1)

Publication Number Publication Date
JPH02163132A true JPH02163132A (en) 1990-06-22

Family

ID=18086034

Family Applications (1)

Application Number Title Priority Date Filing Date
JP31723988A Pending JPH02163132A (en) 1988-12-15 1988-12-15 Molding method of vinylidene fluoride polymer composition

Country Status (1)

Country Link
JP (1) JPH02163132A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9006565B2 (en) 2008-10-16 2015-04-14 Solvay Specialty Polymers Italy S.P.A. Opaque fluoropolymer composition comprising white pigments for photovoltaic elements of solar cells

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9006565B2 (en) 2008-10-16 2015-04-14 Solvay Specialty Polymers Italy S.P.A. Opaque fluoropolymer composition comprising white pigments for photovoltaic elements of solar cells

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