JP3098058B2 - Method for producing polyimide film - Google Patents
Method for producing polyimide filmInfo
- Publication number
- JP3098058B2 JP3098058B2 JP13570591A JP13570591A JP3098058B2 JP 3098058 B2 JP3098058 B2 JP 3098058B2 JP 13570591 A JP13570591 A JP 13570591A JP 13570591 A JP13570591 A JP 13570591A JP 3098058 B2 JP3098058 B2 JP 3098058B2
- Authority
- JP
- Japan
- Prior art keywords
- inorganic powder
- polyimide film
- dispersion
- dispersant
- present
- 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 - Lifetime
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリイミドフィルムの
製造方法に関し、更に詳しくは、無機粉体の種類の切り
替えに要する労力及び時間を大巾に減少させる、ポリイ
ミドフィルムの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyimide film, and more particularly, to a method for producing a polyimide film which greatly reduces the labor and time required for switching the type of inorganic powder. .
【０００２】[0002]
【従来の技術】樹脂成形材料には、一般に種々の目的で
充填材、硬化剤、滑材、可塑剤、顔料、染料、補強剤、
離型剤等が添加されている。特に、近年の小量多品種化
に伴い、添加すべき充填剤等の品種変更の機会は著しく
増加している。2. Description of the Related Art In general, resin molding materials include fillers, curing agents, lubricants, plasticizers, pigments, dyes, reinforcing agents, and the like for various purposes.
A release agent and the like are added. In particular, with the recent increase in the number and variety of small-quantity products, opportunities for changing the types of fillers and the like to be added have been significantly increased.
【０００３】従来、高粘度のポリアミド酸ドープを用い
たポリイミドフィルムの製造時における無機粉体の混合
に際しては、図３に実線で示す如く、該ドープの粘度が
高くなる前の工程、即ち重合工程での増粘終了以前に無
機粉体を添加混合している。しかし、この製造方法で
は、ポリイミドフィルムへの無機粉体添加物の品種変更
及び無機粉体無添加のポリイミドフィルムへ切り替えの
際、重合工程から成形に至る全工程を清掃する必要があ
り、多大の労力と時間が必要となる。Conventionally, when mixing inorganic powder in the production of a polyimide film using a high-viscosity polyamic acid dope, as shown by the solid line in FIG. 3, a step before the viscosity of the dope becomes high, ie, a polymerization step The inorganic powder is added and mixed before the end of thickening in the above. However, in this production method, when changing the type of the inorganic powder additive to the polyimide film and switching to the polyimide film without the addition of the inorganic powder, it is necessary to clean the entire process from the polymerization process to the molding, which is a great deal of work. It requires labor and time.
【０００４】[0004]
【発明が解決しようとする課題】ポリイミドフィルムへ
の無機粉体添加物の品種変更及び無添加ポリイミドフィ
ルムへの切り替えに要する時間は、通常２０〜２００時
間にも達する。そこで、本発明者らは、図３に示す従来
のポリイミドフィルムへの無機粉体添加法において、破
線で示すように、無機粉体を樹脂成形の直前で混合する
ことによって、上記変更・切り替え時の労力、所要時間
を減少させようと試みた。The time required for changing the type of the inorganic powder additive to the polyimide film and switching to the non-added polyimide film usually reaches 20 to 200 hours. In view of the above, in the conventional method of adding inorganic powder to a polyimide film shown in FIG. Tried to reduce the labor and time required.
【０００５】しかし乍ら、成形直前のポリアミド酸ドー
プの高粘度ドープ中へ無機粉体を直接添加混合する場
合、該ドープと無機粉体を安定且つ均一に混合すること
は非常に難しい。即ち、これを敢えて行おうとする場
合、混合装置としてヘリカルリボン羽根、アンカー羽根
等を備えた攪拌槽やボールミル、サンドミル、捏和機な
どが必要であり、いきおい設備が大がかりとなるばかり
でなく、攪拌熱により樹脂が硬化するという心配もあ
る。本発明は上記問題を解決し、上記切り替えに要する
労力及び時間を大巾に減少させるポリイミドフィルムの
製造方法を提供するものである。However, when the inorganic powder is directly added and mixed into the high-viscosity dope of the polyamic acid dope immediately before molding, it is very difficult to stably and uniformly mix the dope and the inorganic powder. That is, if this is intentionally attempted, a mixing device such as a helical ribbon blade, a stirring tank equipped with anchor blades, a ball mill, a sand mill, a kneading machine, and the like are required. There is also a concern that the resin will be cured by heat. The present invention solves the above problems, and provides a method for producing a polyimide film, which significantly reduces the labor and time required for the switching.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、かかる実
情に鑑み鋭意研究の結果、予め無機粉体をある溶媒中に
均一分散させた分散液を用意し、この分散液と重合増粘
の終了したポリアミド酸ドープとを成形直前において混
合することにより、上記問題が解決されることを見出
し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of such circumstances, and as a result, prepared a dispersion in which inorganic powder was uniformly dispersed in a certain solvent in advance, and prepared this dispersion and polymerization thickening. It has been found that the above problem can be solved by mixing the polyamic acid dope, which has been completed, immediately before molding, and the present invention has been completed.
【０００７】即ち、本発明は予め無機粉体を均一分散さ
せた分散液を調製し、ポリアミド酸ドープと前記分散液
とを成形直前で混合することを特徴とするポリイミドフ
ィルムの製造方法を内容とするものである。That is, the present invention relates to a method for producing a polyimide film, which comprises preparing a dispersion in which inorganic powder is uniformly dispersed in advance, and mixing the polyamic acid dope and the dispersion immediately before molding. Is what you do.
【０００８】以下、本発明を詳細に説明する。本発明
は、図１に示す如く、高粘度のポリアミド酸ドープと無
機粉体とを安定且つ均一に混合するために、まず無機粉
体の均一分散液を作り、該分散液とドープとを液液混合
することを特徴の一つとしている。かかる方法によれ
ば、混合及び成形工程のみを清掃すればよい。この液液
混合を行なうに当たっては、無機粉体の分散液が安定的
且つ均一であることが必要である。無機粉体を分散させ
る溶媒は、該ドープの溶媒と同じものを用いるのが望ま
しい。Hereinafter, the present invention will be described in detail. In the present invention, as shown in FIG. 1, in order to stably and uniformly mix a high-viscosity polyamic acid dope and an inorganic powder, a uniform dispersion of the inorganic powder is first prepared, and the dispersion and the dope are mixed with each other. Liquid mixing is one of the features. According to such a method, only the mixing and molding steps need to be cleaned. In performing the liquid-liquid mixing, it is necessary that the dispersion of the inorganic powder is stable and uniform. As the solvent in which the inorganic powder is dispersed, it is desirable to use the same solvent as the solvent of the dope.
【０００９】本発明における無機粉体は、一次粒径１nm
〜１００μｍが好ましく、特に１０nm〜１０μｍが好ま
しい。分散させる無機粉体種にもよるが、無機粉体単独
で安定な均一分散を達成できない場合には、分散剤を用
いるか、または粉体の表面処理を行う必要がある。The inorganic powder according to the present invention has a primary particle size of 1 nm.
To 100 μm, particularly preferably 10 nm to 10 μm. Although it depends on the kind of the inorganic powder to be dispersed, when a stable uniform dispersion cannot be achieved by the inorganic powder alone, it is necessary to use a dispersant or to perform a surface treatment of the powder.
【００１０】分散剤としては、非晶性の超微粒子状の酸
化ケイ素（一次粒子平均径；５〜５０nm）が特に好まし
い。ただし、分散媒が極性溶媒である場合は、超微粒子
状の酸化ケイ素と超微粒子状のアルミナ（一次粒子平均
径；５〜５０nm）との混合物を分散剤として用いるのが
良い。例えば、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭ
Ｆ）中に酸化チタン（ＴｉＯ2 、一次粒子平均径；１〜
５μｍ）を分散させる場合には、ＤＭＦ１００ｇ中に超
微粒子状の酸化ケイ素と超微粒子状のアルミナの混合物
を分散剤として混合することにより、ＴｉＯ2 をＤＭＦ
中に安定且つ均一に分散することができる。分散剤の濃
度は１〜１０重量％が好ましく、１重量％未満では酸化
チタンが沈降してしまい、また１０重量％を越えると液
がゲル状となり流動性が著しく悪くなる。As the dispersant, amorphous ultrafine silicon oxide (average primary particle diameter: 5 to 50 nm) is particularly preferred. However, when the dispersion medium is a polar solvent, a mixture of ultrafine silicon oxide and ultrafine alumina (average primary particle diameter: 5 to 50 nm) is preferably used as a dispersant. For example, N, N-dimethylformamide (DM
F) contains titanium oxide (TiO 2 , average primary particle diameter;
In the case of dispersing TiO 2 in 100 g of DMF, a mixture of ultrafine silicon oxide and ultrafine alumina is mixed as a dispersing agent in
It can be stably and uniformly dispersed therein. The concentration of the dispersant is preferably 1 to 10% by weight, and if it is less than 1% by weight, the titanium oxide precipitates. If it exceeds 10% by weight, the liquid becomes gel-like and the fluidity is remarkably deteriorated.
【００１１】分散剤を用いて無機粉体の分散液を作るに
は、まず分散媒を容器に入れ、そこへ所定量の無機粉体
と分散剤を入れ、ホモミキサー等により高剪断力を加え
て数分間攪拌する。具体的には、例えば特殊機化工業株
式会社製のＴ．Ｋ．オートホモミキサーＭ型を用い、５
０００〜１００００r.p.m.にて１〜６０分攪拌すること
によって安定且つ均一な分散液を作ることができる。表
面処理により分散性を向上させたものとしては、例えば
石原薬品株式会社製のＣＲ−８０（商品名、酸化チタン
の表面をＡｌ，Ｓｉにて処理したもの）がある。表面処
理した無機粉体を用いた分散液作製法は、上記分散剤を
用いる場合と同様である。In order to prepare a dispersion of inorganic powder using a dispersant, a dispersion medium is first placed in a container, a predetermined amount of the inorganic powder and the dispersant are placed therein, and a high shear force is applied thereto using a homomixer or the like. And stir for a few minutes. Specifically, for example, T.K. K. Using an auto homomixer M type, 5
By stirring at 000 to 10000 rpm for 1 to 60 minutes, a stable and uniform dispersion can be produced. As a material having improved dispersibility by the surface treatment, for example, there is CR-80 (trade name, a surface of titanium oxide treated with Al or Si) manufactured by Ishihara Pharmaceutical Co., Ltd. The method for preparing a dispersion using the surface-treated inorganic powder is the same as the method using the above-mentioned dispersant.
【００１２】無機粉体分散液とポリアミド酸ドープとの
混合は、例えば特開平１−２３６９２８、同１−２０７
０２１、同１−２６３０１２に開示されている二液混合
装置を用いることが好ましいが、スタティックミキサー
等を用いても混合することができる。The mixing of the inorganic powder dispersion and the polyamic acid dope is described, for example, in Japanese Patent Application Laid-Open Nos. 1-236928 and 1-207.
It is preferable to use the two-liquid mixing device disclosed in Nos. 021 and 1-263012, but mixing can also be performed using a static mixer or the like.
【００１３】以下、本発明を硬化促進剤を用いて化学的
にイミド化させるポリイミドフィルムの製造工程を例に
挙げて説明する。従来の、無機粉体を添加するポリイミ
ドフィルムの製造フローを図４に示した。この製法で
は、無機粉体の品種切り替えの際には、重合工程からキ
ャストに至るまでの全ての設備を清掃する必要がある。
これに対し、図２に示した如き、本発明の製法を用いた
場合は、混合攪拌とキャストの２工程のみを清掃すれば
よく、切り替え所要時間は約１／６に短縮される。ま
た、本発明において、ポリアミド酸ドープと無機粉体の
分散液と硬化促進剤との混合は、従来法で用いられる攪
拌機でよい。図２と図４との比較から判るように、ポリ
イミドフィルム製造工程においては、大幅なプロセスの
変更を行なうことなく、本発明の無機粉体添加法を適用
することができる。Hereinafter, the present invention will be described by way of an example of a process for producing a polyimide film which is chemically imidized using a curing accelerator. FIG. 4 shows a conventional production flow of a polyimide film to which an inorganic powder is added. In this production method, when changing the type of inorganic powder, it is necessary to clean all equipment from the polymerization step to the casting.
On the other hand, when the production method of the present invention is used as shown in FIG. 2, only the two steps of mixing, stirring and casting need to be cleaned, and the time required for switching is reduced to about 1/6. In the present invention, the mixing of the polyamic acid dope, the dispersion of the inorganic powder, and the curing accelerator may be performed by a stirrer used in a conventional method. As can be seen from a comparison between FIG. 2 and FIG. 4, the inorganic powder addition method of the present invention can be applied to the polyimide film manufacturing process without any significant process change.
【００１４】[0014]
【実施例】次に、実験例を示し、本発明を更に詳細に説
明するが、本発明はこれらにのみ限定されるものではな
い。EXAMPLES Next, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited to these examples.
【００１５】実験例 まず表１の処方で混合し、Ｔ．Ｋ．オートホモミキサー
にて７０００r.p.m.×１０分間攪拌し、酸化チタンのＤ
ＭＦ分散液を作製した。なお、使用した酸化ケイ素、ア
ルミナは、ともに一次粒子平均径が５〜５０nmのもの、
また酸化チタンは一次平均粒子径が１〜５μｍのもので
ある。この酸化チタンの分散液と増粘終了後のポリアミ
ド酸ドープを重量比１：１０で図２に示した本発明プロ
セスにて混合し、２５μｍ厚のフィルムに成形した。そ
の後、酸化チタンを添加しない成形材料に切り替えた
が、時間は約４時間で、比較実験例の場合に比べ約１／
６であった。得られたフィルムの物性値を測定し、その
結果を表２に示した。EXPERIMENTAL EXAMPLE First, mixing was performed according to the formulation shown in Table 1; K. The mixture was stirred at 7000 rpm for 10 minutes with an auto homomixer, and the titanium oxide D
An MF dispersion was prepared. The silicon oxide and alumina used both had an average primary particle diameter of 5 to 50 nm,
The titanium oxide has a primary average particle diameter of 1 to 5 μm. The titanium oxide dispersion and the polyamic acid dope after the completion of thickening were mixed at a weight ratio of 1:10 by the process of the present invention shown in FIG. 2 to form a film having a thickness of 25 μm. After that, the molding material was switched to a molding material to which titanium oxide was not added.
It was 6. The physical properties of the obtained film were measured, and the results are shown in Table 2.
【００１６】比較実験例 低粘度時に既に酸化チタンを分散させたポリアミド酸ド
ープを用いて、図４に示した従来プロセスにて２５μｍ
厚のフィルムを成形した。得られたフィルムの物性値を
測定し、その結果を表２に示した。その後、酸化チタン
を添加しない成形材料に切り替えたが、約２４時間を要
した。Comparative Experimental Example Using a polyamic acid dope in which titanium oxide was already dispersed at a low viscosity, the conventional process shown in FIG.
Thick films were formed. The physical properties of the obtained film were measured, and the results are shown in Table 2. Thereafter, the molding material was switched to a molding material to which titanium oxide was not added, but it took about 24 hours.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【発明の効果】本発明は、無機粉体を添加するポリイミ
ドフィルムの製造において粉体の品種の切り替えに要す
る労力及び時間を大幅に減少し、小量多品種の市場ニー
ズに応えるポリイミドフィルムを提供することができ
る。According to the present invention, there is provided a polyimide film which can meet the market needs of small quantity and many kinds by greatly reducing the labor and time required for changing the kind of the powder in the production of the polyimide film to which the inorganic powder is added. can do.
【図１】本発明による、ポリイミドフィルムへの無機粉
体の添加フローを示す。FIG. 1 shows a flow of adding an inorganic powder to a polyimide film according to the present invention.
【図２】本発明による、ポリイミドフィルムの製造フロ
ーを示す。FIG. 2 shows a production flow of a polyimide film according to the present invention.
【図３】従来法による、ポリイミドフィルムへの無機粉
体の添加フローを示す。FIG. 3 shows a flow of adding an inorganic powder to a polyimide film according to a conventional method.
【図４】従来法による、ポリイミドフィルムの製造フロ
ーを示す。FIG. 4 shows a production flow of a polyimide film according to a conventional method.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 3/00 - 3/28 C08J 5/18 C08L 1/00 - 101/16 ──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int. Cl. 7 , DB name) C08J 3/00-3/28 C08J 5/18 C08L 1/00-101/16
Claims (7)
調製し、ポリアミド酸ドープと前記分散液とを成形直前
で混合することを特徴とするポリイミドフィルムの製造
方法。1. A method for producing a polyimide film, comprising preparing a dispersion in which inorganic powder is uniformly dispersed in advance, and mixing the polyamic acid dope and the dispersion immediately before molding.
促進剤の添加の工程でポリアミド酸ドープに混合する請
求項１記載の製造方法。2. The production method according to claim 1, wherein the dispersion in which the inorganic powder is uniformly dispersed is mixed with the polyamic acid dope in the step of adding the curing accelerator.
１記載の製造方法。3. The production method according to claim 1, wherein the dispersion is prepared using a dispersant.
項１又は３記載の製造方法。4. The method according to claim 1, wherein the inorganic powder is surface-treated.
アルミナの混合物である請求項３記載の製造方法。5. The method according to claim 3, wherein the dispersant is silicon oxide or a mixture of silicon oxide and alumina.
０μｍである請求項１記載の製造方法。6. The inorganic powder has a primary particle diameter of 1 nm to 10 nm.
The method according to claim 1, wherein the thickness is 0 µm.
請求項３又は５記載の製造方法。7. The method according to claim 3, wherein the dispersant has a primary particle size of 5 to 50 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13570591A JP3098058B2 (en) | 1991-05-10 | 1991-05-10 | Method for producing polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13570591A JP3098058B2 (en) | 1991-05-10 | 1991-05-10 | Method for producing polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04335037A JPH04335037A (en) | 1992-11-24 |
| JP3098058B2 true JP3098058B2 (en) | 2000-10-10 |
Family
ID=15157964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13570591A Expired - Lifetime JP3098058B2 (en) | 1991-05-10 | 1991-05-10 | Method for producing polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3098058B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012111970A (en) * | 2012-03-22 | 2012-06-14 | Toshiba Corp | Alumina-containing two-pack casting resin composition, method for producing the same, and gas insulation switch gear |
| JP2014148126A (en) * | 2013-02-01 | 2014-08-21 | Kaneka Corp | Method for producing polyimide film |
-
1991
- 1991-05-10 JP JP13570591A patent/JP3098058B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04335037A (en) | 1992-11-24 |
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