JPH05202204A - Polymide prepreg for laminating - Google Patents
Polymide prepreg for laminatingInfo
- Publication number
- JPH05202204A JPH05202204A JP4032696A JP3269692A JPH05202204A JP H05202204 A JPH05202204 A JP H05202204A JP 4032696 A JP4032696 A JP 4032696A JP 3269692 A JP3269692 A JP 3269692A JP H05202204 A JPH05202204 A JP H05202204A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- polyimide
- varnish
- polyimide resin
- solvent
- 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
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、安定性のよいポリイミ
ド系樹脂ワニスを用い、含浸性に優れ、特に塗りむらが
なく、積層外観のよい積層用ポリイミドプリプレグに関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide prepreg for lamination, which uses a highly stable polyimide resin varnish, has excellent impregnation properties, is free from uneven coating, and has a good laminated appearance.
【０００２】[0002]
【従来の技術】電子機器の発達に伴い、それらに使用さ
れるプリント配線板の特性に対する要求はますます厳し
くなっており、特に耐熱性が要求される場合は、配線板
の基板としてポリイミド系樹脂積層板が使用されてい
る。ここに使用されるポリイミド系樹脂は、溶剤への溶
解性が低く、また溶解したワニスの粘度が高いために、
基材への含浸性が悪く、プリプレグに塗りむらが生じる
等の欠点がある。また、この樹脂のプリプレグを用いて
積層板を製造する場合に成形性が悪く、例えば、ボイド
が発生する、周辺がかすれる等の欠点がある。このよう
にポリイミド系樹脂は、溶解性等が悪いため、プリプレ
グを製造する場合、使用される溶剤は限定され、Ｎ−メ
チル−2-ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、
Ｎ，Ｎ−ジメチルホルムアミド等のアミド系溶剤、ジオ
キサン、メチルセロソルブ等のエチレングリコール系溶
剤が用いられている。2. Description of the Related Art With the development of electronic devices, the demands on the characteristics of printed wiring boards used for them have become more and more stringent. Especially when heat resistance is required, a polyimide resin is used as a substrate for wiring boards. Laminates are used. The polyimide resin used here has a low solubility in a solvent, and the viscosity of the dissolved varnish is high,
There are drawbacks such as poor impregnation into the substrate and uneven coating on the prepreg. In addition, when a prepreg of this resin is used to manufacture a laminated plate, the formability is poor, and there are drawbacks such as the occurrence of voids and fading of the periphery. As described above, since the polyimide-based resin has poor solubility and the like, when producing a prepreg, the solvent used is limited, and N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Amide solvents such as N, N-dimethylformamide and ethylene glycol solvents such as dioxane and methyl cellosolve are used.
【０００３】アミド系溶剤は、溶解性は高く、プリプレ
グの含浸性や塗りむらを改善できるが、極性が高いため
ワニスの安定性に劣る問題がある。すなわち、溶剤の高
い極性が樹脂に対し硬化促進の作用を示し、ワニスの可
使時間を短くする欠点がある。また、エチレングリコー
ル系溶剤は、低極性でワニスの安定性には問題がないも
のの、アミド系溶剤に比較して溶解性に劣るため、含浸
性が悪く、塗りむら、発泡等を生じてプリプレグの外観
を損ねる欠点がある。また、最近では、環境汚染、安全
性の問題等により、ジオキサン、エチレングリコール系
溶剤は、使用が制限される等の問題が起きてきた。The amide-based solvent has high solubility and can improve impregnation property and uneven coating of the prepreg, but has a problem that the varnish is inferior in stability because of its high polarity. That is, there is a drawback that the high polarity of the solvent has the effect of promoting the curing of the resin and shortens the pot life of the varnish. Further, the ethylene glycol-based solvent has low polarity and there is no problem in the stability of the varnish, but since the solubility is inferior to that of the amide-based solvent, impregnating property is poor, and uneven coating, foaming, etc. occur to cause prepreg formation. It has the drawback of impairing the appearance. Further, recently, due to environmental pollution, safety problems, etc., problems such as the use of dioxane and ethylene glycol-based solvents have been restricted have occurred.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記従来の
欠点を解消し、安定性のよいポリイミド系樹脂ワニスを
用いて、含浸性に優れ、塗りむら、発泡等がなく外観の
よい積層用ポリイミドプリプレグを提供しようとするも
のである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional drawbacks and uses a highly stable polyimide resin varnish, which has excellent impregnation property and is free from uneven coating, foaming, etc. It is intended to provide a polyimide prepreg.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記の目的
を達成しようと鋭意研究を重ねた結果、特定の溶剤を用
いることによって、上記目的が達成できることを見いだ
し、本発明を完成させたものである。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by using a specific solvent, and completed the present invention. It is a thing.
【０００６】即ち、本発明は、基材に、ポリイミド系樹
脂ワニスを連続的に含浸・乾燥させてなる積層用プリプ
レグにおいて、前記ポリイミド系樹脂ワニスの溶剤とし
て一般式That is, the present invention relates to a prepreg for lamination in which a base material is continuously impregnated with a polyimide resin varnish and dried, and a general formula is used as a solvent for the polyimide resin varnish.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】（但し、式中Ｒはメチル基またはエチル基
を表す）で示されるジプロピレングリコールモノアルキ
ルエーテルを用いたことを特徴とする積層用ポリイミド
プリプレグである。A polyimide prepreg for lamination, characterized in that a dipropylene glycol monoalkyl ether represented by the formula (wherein R represents a methyl group or an ethyl group) is used.
【０００９】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【００１０】本発明に用いる基材としては、特に制限さ
れるものではないが、ガラスクロス、ガラスペーパー等
のガラス基材、ポリアミド繊維や炭素繊維等の耐熱性良
好な繊維からなる織布又は不織布が好適に使用される。The substrate used in the present invention is not particularly limited, but a glass substrate such as glass cloth or glass paper, or a woven or non-woven fabric made of fibers having good heat resistance such as polyamide fiber or carbon fiber. Is preferably used.
【００１１】本発明に用いるポリイミド系樹脂として
は、通常積層板用としてもちいられるものが広く使用す
ることができる。例えば、縮重合型ポリイミド樹脂、付
加反応型ポリイミド樹脂等及びこれらの変性樹脂等が挙
げられ、これらは単独または 2種以上混合して使用する
ことができる。As the polyimide resin used in the present invention, those generally used for laminated boards can be widely used. Examples thereof include polycondensation type polyimide resin, addition reaction type polyimide resin and the like and modified resins thereof, and these can be used alone or in combination of two or more kinds.
【００１２】本発明に用いる溶剤としては、ポリイミド
系樹脂に対して溶解性のある一般式The solvent used in the present invention is a general formula which has a solubility in polyimide resins.
【００１３】[0013]
【化３】 （但し、式中Ｒはメチル基またはエチル基を表す）で示
されるジプロピレングリコールモノアルキルエーテルが
使用される。ジプロピレングリコールモノアルキルエー
テルの具体的なものとして、ジプロピレングリコールモ
ノメチルエーテル（bp 190℃）、ジプロピレングリコー
ルモノエチルエーテル（bp 198℃）が挙げれ、これらは
単独または 2種混合して使用することができる。ポリイ
ミド系樹脂をジプロピレングリコールモノアルキルエー
テルに溶解して、基材に含浸しやすく、安定性のあるポ
リイミド系樹脂ワニスを得ることができる。このワニス
は、ポリイミド系樹脂をジプロピレングリコールモノア
ルキルエーテルに溶解したものであるが、本発明の目的
に反しない範囲において、また必要に応じて難燃剤、硬
化剤、硬化促進剤、充填剤等を添加配合することができ
る。[Chemical 3] (In the formula, R represents a methyl group or an ethyl group), and dipropylene glycol monoalkyl ether is used. Specific examples of dipropylene glycol monoalkyl ether include dipropylene glycol monomethyl ether (bp 190 ° C) and dipropylene glycol monoethyl ether (bp 198 ° C), which may be used alone or in combination of two types. You can It is possible to obtain a stable polyimide resin varnish by dissolving the polyimide resin in dipropylene glycol monoalkyl ether to easily impregnate the base material. This varnish is a polyimide-based resin dissolved in dipropylene glycol monoalkyl ether, but in a range that does not violate the object of the present invention, and if necessary, a flame retardant, a curing agent, a curing accelerator, a filler, etc. Can be added and compounded.
【００１４】こうして得られたポリイミド系樹脂ワニス
を用いて、上述した基材に含浸・乾燥させて容易に積層
用ポリイミドプリプレグを製造することができる。この
時の乾燥温度は、プリプレグ中の残留溶剤をできる限り
少なくするため、使用した溶剤の沸点に近い温度に設定
することが望ましい。この積層用ポリイミドプリプレグ
は、アミド系溶剤を使用した時と同等の含浸性、外観を
有しており、これを銅箔等と加熱加圧一体に成形して銅
張積層板を製造することができる。Using the polyimide resin varnish thus obtained, the above-mentioned base material is impregnated and dried to easily produce a polyimide prepreg for lamination. The drying temperature at this time is preferably set to a temperature close to the boiling point of the solvent used in order to reduce the residual solvent in the prepreg as much as possible. This laminating polyimide prepreg has the same impregnating property and appearance as when using an amide-based solvent, and it is possible to form a copper clad laminated sheet by integrally molding this with a copper foil and the like under heat and pressure. it can.
【００１５】[0015]
【作用】本発明の積層用ポリイミドプリプレグは、ポリ
イミド系樹脂をジプロピレングリコールモノアルキルエ
ーテルで溶解したことによって安定性のよいワニスが得
られ、また含浸性に優れ、塗りむらがなく、外観のよい
ものを製造することができた。すなわち、ジプピレング
リコールモノアルキルエーテルの優れた溶解性でポリイ
ミド系樹脂ワニスを均一に溶解し、ワニスを基材に含浸
するに適した状態に調整することができる。またジプロ
ピレングリコールモノアルキルエーテルは低極性のた
め、アミド系溶剤のような硬化促進作用はなく、可使時
間の長い安定性に優れたワニスを得ることができる。さ
らに、このワニスを用いることによって、塗りむらがな
く、外観に優れたプリプレグを得ることができる。The polyimide prepreg for lamination according to the present invention has a stable varnish obtained by dissolving a polyimide resin in dipropylene glycol monoalkyl ether, has excellent impregnation property, has no uneven coating, and has a good appearance. It was possible to manufacture things. That is, it is possible to adjust the state suitable for impregnating the substrate with the varnish by uniformly dissolving the polyimide resin varnish with the excellent solubility of dipyrene glycol monoalkyl ether. Further, since dipropylene glycol monoalkyl ether has a low polarity, it does not have a curing-promoting action unlike amide solvents, and a varnish having a long pot life and excellent stability can be obtained. Furthermore, by using this varnish, it is possible to obtain a prepreg having no uneven coating and an excellent appearance.
【００１６】[0016]
【実施例】次に本発明を実施例によって説明するが、本
発明はこれらの実施例によって限定されるものではな
い。以下の実施例及び比較例において「部」とは「重量
部」を意味する。EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, "part" means "part by weight".
【００１７】実施例１ ポリイミド系樹脂（当社製） 100部に、２Ｅ４ＭＺ−Ｃ
Ｎ（四国化成社製イミダゾール、商品名） 5部、および
ジプロピレングリコールモノメチルエーテル20部を加え
て、混合・攪拌してポリイミド系樹脂ワニスを得た。こ
のワニスを用いて、厚さ 180μm のガラスクロスに含浸
し、180 ℃の温度で乾燥し、樹脂分38重量％の積層用ポ
リイミドプリプレグを製造した。Example 1 100 parts of a polyimide resin (made by our company) was added to 2E4MZ-C.
5 parts of N (imidazole manufactured by Shikoku Kasei Co., Ltd., trade name) and 20 parts of dipropylene glycol monomethyl ether were added and mixed and stirred to obtain a polyimide resin varnish. A glass cloth having a thickness of 180 μm was impregnated with this varnish and dried at a temperature of 180 ° C. to produce a polyimide prepreg for lamination having a resin content of 38% by weight.
【００１８】実施例２ 実施例１において、ジプロピレングリコールモノメチル
エーテルの替わりに、ジプロピレングリコールモノエチ
ルエーテルを用い、190 ℃の温度で乾燥した以外は全て
実施例１と同一にして積層用ポリイミドプリプレグを製
造した。Example 2 A polyimide prepreg for lamination was prepared in the same manner as in Example 1 except that dipropylene glycol monoethyl ether was used in place of dipropylene glycol monomethyl ether and drying was carried out at a temperature of 190 ° C. Was manufactured.
【００１９】比較例１ 実施例１において、ジプロピレングリコールモノメチル
エーテルの替わりに、Ｎ−メチル−2-ピロリドンを使用
し、200 ℃の温度で乾燥した以外は全て実施例１と同様
にして積層用ポリイミドプリプレグを製造した。Comparative Example 1 In the same manner as in Example 1, except that N-methyl-2-pyrrolidone was used in place of dipropylene glycol monomethyl ether and drying was carried out at a temperature of 200 ° C. A polyimide prepreg was manufactured.
【００２０】比較例２ 実施例１において、ジプロピレングリコールモノメチル
エーテルの替わりに、ジオキサンを使用し、140 ℃の温
度で乾燥した以外は全て実施例１と同様にして積層用ポ
リイミドプリプレグを製造した。Comparative Example 2 A polyimide prepreg for lamination was produced in the same manner as in Example 1 except that dioxane was used in place of dipropylene glycol monomethyl ether and drying was performed at a temperature of 140 ° C.
【００２１】実施例１〜２及び比較例１〜２で製造した
積層用ポリイミドプリプレグそれぞれについて 9枚を重
ね、その両側に厚さ18μm の銅箔を重ねて、190 ℃の温
度で90分間，40 kgf／cm2 の圧力で加熱加圧成形一体化
して、板厚1.6 mmの銅張積層板を製造した。Nine sheets of each of the laminated polyimide prepregs produced in Examples 1 and 2 and Comparative Examples 1 and 2 were superposed, and copper foil having a thickness of 18 μm was superposed on both sides thereof, and the temperature was set at 190 ° C. for 90 minutes for 40 minutes. A copper-clad laminate having a plate thickness of 1.6 mm was manufactured by heat-press molding under pressure of kgf / cm 2 .
【００２２】ワニス、プリプレグ、銅張積層板につい
て、ワニスの可使時間、プリプレグの外観（含浸性、塗
りむら）、銅張積層板のエッチング後の外観（ボイド、
カスレ）について試験したので、その結果を表１に示し
た。本発明の積層用ポリイミドプリプレグは、全ての特
性に優れており、本発明の効果を確認することができ
た。For varnishes, prepregs, and copper-clad laminates, pot life of varnish, appearance of prepreg (impregnating property, uneven coating), appearance of copper-clad laminate after etching (void,
The result was shown in Table 1. The polyimide prepreg for lamination of the present invention was excellent in all properties, and the effects of the present invention could be confirmed.
【００２３】[0023]
【表１】 ＊1 ：○印…なし、×印…有り。 ＊2 ：○印…良好、×印…悪い。[Table 1] * 1: ○: No, ×: Yes. * 2: ○: Good, ×: Bad.
【００２４】[0024]
【発明の効果】以上の説明及び表１から明らかなよう
に、本発明の積層用ポリイミドプリプレグは、含浸性に
優れ、塗りむらがなく、このプリプレグを用いた銅張積
層板は、ボイド、カスレのない信頼性の高いものであ
る。また、ワニスは、可使時間が長く安定性に優れたも
のである。As is clear from the above description and Table 1, the polyimide prepreg for lamination according to the present invention has excellent impregnation properties and has no uneven coating, and a copper clad laminate using this prepreg has voids, scrapes and There is no reliable one. The varnish has a long pot life and excellent stability.
Claims (1)
的に含浸・乾燥させてなる積層用プリプレグにおいて、
前記ポリイミド系樹脂ワニスの溶剤として一般式 【化１】 （但し、式中Ｒはメチル基またはエチル基を表す）で示
されるジプロピレングリコールモノアルキルエーテルを
用いたことを特徴とする積層用ポリイミドプリプレグ。1. A laminating prepreg obtained by continuously impregnating and drying a base material with a polyimide resin varnish,
As a solvent for the polyimide resin varnish, a general formula: A polyimide prepreg for lamination, characterized by using a dipropylene glycol monoalkyl ether represented by the formula (wherein R represents a methyl group or an ethyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4032696A JPH05202204A (en) | 1992-01-23 | 1992-01-23 | Polymide prepreg for laminating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4032696A JPH05202204A (en) | 1992-01-23 | 1992-01-23 | Polymide prepreg for laminating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05202204A true JPH05202204A (en) | 1993-08-10 |
Family
ID=12366020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4032696A Pending JPH05202204A (en) | 1992-01-23 | 1992-01-23 | Polymide prepreg for laminating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05202204A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10941320B2 (en) * | 2014-08-08 | 2021-03-09 | Toray Industries, Inc. | Adhesive for temporary bonding, adhesive layer, wafer work piece and method for manufacturing semiconductor device using same, rework solvent, polyimide copolymer, polyimide mixed resin, and resin compostion |
-
1992
- 1992-01-23 JP JP4032696A patent/JPH05202204A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10941320B2 (en) * | 2014-08-08 | 2021-03-09 | Toray Industries, Inc. | Adhesive for temporary bonding, adhesive layer, wafer work piece and method for manufacturing semiconductor device using same, rework solvent, polyimide copolymer, polyimide mixed resin, and resin compostion |
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