JPH06345864A - Thermosetting resin composition, production of prepreg and production of laminated board - Google Patents
Thermosetting resin composition, production of prepreg and production of laminated boardInfo
- Publication number
- JPH06345864A JPH06345864A JP14101993A JP14101993A JPH06345864A JP H06345864 A JPH06345864 A JP H06345864A JP 14101993 A JP14101993 A JP 14101993A JP 14101993 A JP14101993 A JP 14101993A JP H06345864 A JPH06345864 A JP H06345864A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- cyanate ester
- thermosetting resin
- resin composition
- production
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プリント配線板等の絶
縁材料として有用な熱硬化性樹脂組成物と、この熱硬化
性樹脂組成物を用いたプリプレグの製造方法、及びこの
プリプレグを用いた積層板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition useful as an insulating material for printed wiring boards and the like, a method for producing a prepreg using the thermosetting resin composition, and the prepreg. The present invention relates to a method for manufacturing a laminated board.
【０００２】[0002]
【従来の技術】近年、電子機器、特に通信、コンピュー
タの分野では情報処理の高速化が要求され、この要求に
対応するために、プリント配線板の絶縁層を低誘電率化
することが試みられている。このプリント配線板の絶縁
層を低誘電率化するために、プリント配線板の絶縁材料
として、多官能性シアネートエステル類を単に加熱する
か、又は硬化触媒の存在化で加熱することによりシアネ
ートエステル基を三量化せしめて得られるトリアジン環
を有する熱硬化性樹脂を用いて絶縁層を形成すると有効
であることが知られている。しかしながら、この種のシ
アネートエステル樹脂の硬化物は、耐熱性、誘電特性、
及び電気絶縁性などに優れているが、吸湿性が大きいと
いう欠点を有している。その結果、絶縁層の誘電率や誘
電正接等の誘電特性が、吸湿後には当初の優れた値に比
較して大きく劣化するという問題を生ずる。さらに、こ
の吸湿した硬化物の成形体が急激に加熱されると、吸収
された水分が気化膨張し、成形体表面にクラックを発生
するという問題も生ずる。このクラックの発生は、例え
ばプリント配線板において、絶縁体表面に形成された回
路を断線させる原因となるので、致命的な欠陥である。
したがって、上記に述べた如く、シアネートエステル樹
脂の吸湿性は、シアネートエステル樹脂の硬化物が常態
で本来有する優れた特性を大きく損なう原因となってい
る。2. Description of the Related Art In recent years, there has been a demand for high-speed information processing in the fields of electronic equipment, particularly communications and computers, and in order to meet this demand, attempts have been made to lower the dielectric constant of the insulating layer of printed wiring boards. ing. In order to lower the dielectric constant of the insulating layer of this printed wiring board, as the insulating material of the printed wiring board, polyfunctional cyanate esters are simply heated, or by heating in the presence of a curing catalyst, a cyanate ester group is formed. It is known that it is effective to form an insulating layer by using a thermosetting resin having a triazine ring obtained by trimerizing. However, a cured product of this type of cyanate ester resin has heat resistance, dielectric properties,
Although it is excellent in electric insulation and the like, it has a drawback that it has high hygroscopicity. As a result, there arises a problem that the dielectric properties such as the dielectric constant and the dielectric loss tangent of the insulating layer are significantly deteriorated after absorbing moisture as compared with the initially excellent values. Further, when the molded body of the moisture-absorbed cured product is rapidly heated, the absorbed water vaporizes and expands, which causes a problem that cracks are generated on the surface of the molded body. The occurrence of this crack is a fatal defect because it causes a disconnection of a circuit formed on the surface of an insulator in a printed wiring board, for example.
Therefore, as described above, the hygroscopicity of the cyanate ester resin is a cause of greatly impairing the excellent properties originally possessed by the cured product of the cyanate ester resin.
【０００３】[0003]
【発明が解決しようとする課題】上記の事情に鑑みて、
本発明は、シアネートエステル樹脂の硬化物が本来有す
る誘電特性を保持しながら欠点である吸湿性を低減し
て、誘電特性の劣化の抑制と耐クラック性の向上がなさ
れた熱硬化性樹脂組成物と、この熱硬化性樹脂組成物を
用いたプリプレグの製造方法、及びこのプリプレグを用
いた積層板の製造方法を提供するものである。In view of the above circumstances,
The present invention is a thermosetting resin composition in which the defect hygroscopicity is reduced while retaining the dielectric properties originally possessed by a cured product of a cyanate ester resin, and deterioration of the dielectric properties is suppressed and crack resistance is improved. And a method for producing a prepreg using the thermosetting resin composition, and a method for producing a laminated board using the prepreg.
【０００４】[0004]
【課題を解決するための手段】本発明の熱硬化性樹脂組
成物は、多官能性シアネートエステル、モノマレイミド
化合物、及び上記シアネートエステルの反応触媒を含有
して成ることを特徴とするものと、多官能性シアネート
エステル、モノマレイミド化合物、ポリフェニレンオキ
サイド（以下ＰＰＯとする）、及び上記シアネートエス
テルの反応触媒を含有して成ることを特徴とするもので
ある。The thermosetting resin composition of the present invention is characterized by comprising a polyfunctional cyanate ester, a monomaleimide compound, and a reaction catalyst of the above cyanate ester, It is characterized by containing a polyfunctional cyanate ester, a monomaleimide compound, polyphenylene oxide (hereinafter referred to as PPO), and a reaction catalyst of the above cyanate ester.
【０００５】他の発明に係るプリプレグの製造方法は、
この熱硬化性樹脂組成物を基材に含浸し、加熱乾燥して
半硬化させる点に特徴を有し、さらに他の発明に係る積
層板の製造方法は、このプリプレグを積層成形する点に
特徴を有する。A method of manufacturing a prepreg according to another invention is
The thermosetting resin composition is impregnated into a base material, which is characterized by being heated and dried to be semi-cured, and a method for manufacturing a laminated board according to another invention is characterized in that the prepreg is laminated and molded. Have.
【０００６】以下、本発明を詳細に説明すると、本発明
において用いられる多官能性シアネートエステルとして
は、２個以上のシアネートエステル基を有する任意の有
機化合物であり、例えばこの有機化合物の一例を示すと
（化１）の一般式で表される。The present invention will be described in detail below. The polyfunctional cyanate ester used in the present invention is any organic compound having two or more cyanate ester groups, and one example of this organic compound is shown below. It is represented by the general formula of (Chemical Formula 1).
【０００７】[0007]
【化１】 [Chemical 1]
【０００８】上記有機基Ｒは、炭素数６〜１６の芳香族
炭化水素より誘導される有機基であっても、或いは複数
個の芳香族炭化水素基が橋絡原子又は基を介して結合し
た有機基であっても、或いはポリシロキサンであっても
よい。Ｒがポリシロキサンであるシアネートエステルの
一例を示すと（化２）の一般式で表される。The above-mentioned organic group R may be an organic group derived from an aromatic hydrocarbon having 6 to 16 carbon atoms, or a plurality of aromatic hydrocarbon groups bonded via a bridging atom or a group. It may be an organic group or polysiloxane. An example of a cyanate ester in which R is a polysiloxane is represented by the general formula (Formula 2).
【０００９】[0009]
【化２】 [Chemical 2]
【００１０】本発明において使用される前述の多官能性
シアネートエステルは、所謂モノマーであっても、プレ
ポリマーであっても、或いはモノマーとプレポリマーの
混合物であってもよい。例えば、商業的に入手できる、
ビスフェノールＡとハロゲン化シアンの反応により得ら
れるシアネートエステルは、そのモノマーとプレポリマ
ーの混合物の形態をしている場合が多いが、このような
シアネートエステルは本発明において用いられる代表的
なシアネートエステルである。The aforementioned polyfunctional cyanate ester used in the present invention may be a so-called monomer, a prepolymer, or a mixture of a monomer and a prepolymer. For example, commercially available,
The cyanate ester obtained by the reaction of bisphenol A and a cyanogen halide is often in the form of a mixture of its monomer and a prepolymer. Such a cyanate ester is a typical cyanate ester used in the present invention. is there.
【００１１】本発明の特徴は、シアネートエステル樹脂
の硬化物の欠点である吸湿性を低減させることを目的と
して、モノマレイミド化合物を樹脂成分として含有させ
る点にある。。この吸湿性を低減させることにより、樹
脂硬化物の吸湿による誘電特性の劣化を抑制し、同時に
吸湿した水の加熱時の気化膨張による積層板のクラック
発生を防止するものである。本発明に用いられるモノマ
レイミド化合物の代表的な一例を（化３）に示す。A feature of the present invention is that a monomaleimide compound is contained as a resin component for the purpose of reducing hygroscopicity which is a defect of a cured product of a cyanate ester resin. . By reducing this hygroscopicity, deterioration of the dielectric properties due to moisture absorption of the resin cured product is suppressed, and at the same time, the occurrence of cracks in the laminated plate due to vaporization and expansion during heating of the moisture absorbed water is prevented. A typical example of the monomaleimide compound used in the present invention is shown in (Chemical Formula 3).
【００１２】[0012]
【化３】 [Chemical 3]
【００１３】ここで、Ｒはフェニル基又は活性水素を含
まない芳香族基の誘導体であり、例えば、（化４）に示
した有機基等である。Here, R is a derivative of a phenyl group or an aromatic group containing no active hydrogen, and is, for example, the organic group shown in (formula 4).
【００１４】[0014]
【化４】 [Chemical 4]
【００１５】このモノマレイミド化合物は、配合したシ
アネートエステルとモノマレイミド化合物の合計量に対
し１０〜５０重量％の範囲の量で配合されるのが好まし
い。その理由として、モノマレイミド化合物の配合量が
配合したシアネートエステルとモノマレイミド化合物の
合計量に対し１０重量％以下であると耐クラック性の改
善が期待できず、５０重量％以上であると積層板の誘電
特性が損なわれるという問題を生じる可能性があるから
である。The monomaleimide compound is preferably added in an amount in the range of 10 to 50% by weight based on the total amount of the cyanate ester and the monomaleimide compound. The reason is that crack resistance cannot be expected to be improved when the amount of the monomaleimide compound is 10% by weight or less based on the total amount of the cyanate ester and the monomaleimide compound blended, and when it is 50% by weight or more, the laminated sheet This may cause a problem of impairing the dielectric properties of.
【００１６】また、本発明において、配合するモノマレ
イミド化合物として、例えば、（化４）のＲ1 がＢｒで
あるようなハロゲン化された有機基を有するものを用い
た場合、積層板に難燃性を付与することができる。ＵＬ
規格の９４Ｖ−０のレベルの難燃性を得るにも、上記の
モノマレイミド化合物の配合量で十分である。Further, in the present invention, when the monomaleimide compound to be blended is, for example, one having a halogenated organic group in which R 1 of (Chemical Formula 4) is Br, flame retardancy is imparted to the laminate. It is possible to impart sex. UL
The blending amount of the above-mentioned monomaleimide compound is sufficient for obtaining the flame retardancy of the standard level of 94V-0.
【００１７】本発明の特徴は、さらに多官能性シアネー
トエステルを重合させる反応触媒を含有させる点にあ
る。この反応触媒として例示すると、イミダゾール類、
第三級アミン、有機金属塩類等を用いることができるも
のであり、特にナフテン酸コバルトやオクチル酸コバル
ト等の有機コバルト塩類が好ましい。反応触媒の配合量
についても、後述するワニスの所望するゲル化時間が得
れるように配合するのが望ましい。The feature of the present invention is that it further contains a reaction catalyst for polymerizing the polyfunctional cyanate ester. Examples of this reaction catalyst include imidazoles,
Tertiary amines, organic metal salts and the like can be used, and organic cobalt salts such as cobalt naphthenate and cobalt octylate are particularly preferable. The amount of the reaction catalyst to be blended is preferably such that the desired gelling time of the varnish described later can be obtained.
【００１８】本発明の熱硬化性樹脂組成物においては、
樹脂成分として、前述のシアネートエステルとモノマレ
イミド化合物に、さらにＰＰＯを配合してもよい。この
場合、ＰＰＯはＰＰＯを含む樹脂成分の全体に対して０
〜５０重量％の範囲で配合されるのが好ましい。すなわ
ち、ＰＰＯを樹脂成分として含有させると、この熱硬化
性樹脂組成物を用いて得られた積層板の誘電特性を損な
わず、かつ吸湿性を増大させることなく積層板の板厚精
度を向上させることができる。ここで、ＰＰＯの一例を
一般式で（化５）に示す。In the thermosetting resin composition of the present invention,
As the resin component, PPO may be further added to the above cyanate ester and monomaleimide compound. In this case, PPO is 0 with respect to the entire resin component containing PPO.
It is preferably blended in the range of 50% by weight. That is, when PPO is contained as a resin component, the plate thickness accuracy of the laminate is improved without impairing the dielectric properties of the laminate obtained using this thermosetting resin composition and without increasing the hygroscopicity. be able to. Here, an example of PPO is shown by the general formula (Formula 5).
【００１９】[0019]
【化５】 [Chemical 5]
【００２０】本発明の熱硬化性樹脂組成物は、基材に含
浸してプリプレグを得るために、まず前述の樹脂成分及
び反応触媒を有機溶媒に溶解し、ワニスに調製して用い
られる。この有機溶媒としては、樹脂成分を溶解し、か
つ反応に悪影響を及ぼすものでなければ特に限定され
ず、例えば、メチルエチルケトン等のケトン類、ジブチ
ルエーテル等のエーテル類、酢酸エチル等のエステル
類、ジメチルホルムアミド等のアミド類、トリクロロエ
チレン等の塩素化炭化水素等の適当な不活性有機溶媒を
一種或いは二種以上を混合して用いられる。上記ワニス
中の樹脂固形分の濃度は、ワニスを基材に含浸する作業
性に応じて適当に調製すればよく、例えば５０〜９０重
量％が適当である。In order to obtain a prepreg by impregnating a base material, the thermosetting resin composition of the present invention is used by first dissolving the above-mentioned resin component and reaction catalyst in an organic solvent to prepare a varnish. The organic solvent is not particularly limited as long as it dissolves the resin component and does not adversely affect the reaction, and examples thereof include ketones such as methyl ethyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate, and dimethyl. Suitable inert organic solvents such as amides such as formamide and chlorinated hydrocarbons such as trichloroethylene are used alone or in combination of two or more. The concentration of the resin solid content in the varnish may be appropriately adjusted according to the workability of impregnating the base material with the varnish, and for example, 50 to 90% by weight is suitable.
【００２１】上記の如く調製されたワニスを基材に含浸
し、さらに加熱乾燥し有機溶媒を蒸発させてプリプレグ
を得る。上記の基材としては、有機繊維やガラス繊維の
織布または不織布を用いるのがこれまでの積層板として
は一般的である。この基材へのワニスの含浸量は、プリ
プレグ中の樹脂固形分の重量比率が３５重量％以上にな
るようにするのが好ましい。一般に基材の誘電率は樹脂
のそれよりも大きく、それゆえに、プリプレグ中の樹脂
固形分の含有量が少ないと、このプリプレグを用いて得
られた積層板の誘電率は大きくなる。例えば、基材にＥ
ガラス布を用いたプリプレグが３７重量％以上の樹脂固
形分の含有量では誘電率３．７以下を達成することがで
き、基材にＤガラス布を用いたプリプレグが４５重量％
以上の樹脂固形分の含有量では誘電率３．２以下を達成
することができる。なお、本発明においては、プリプレ
グを調製する際の加熱乾燥条件は、使用する反応触媒の
種類や配合量により異なってくるが、プリプレグに含有
される樹脂組成物の所望のゲル化時間が得られるように
加熱乾燥条件を設定すればよい。A prepreg is obtained by impregnating a base material with the varnish prepared as described above, further drying by heating to evaporate the organic solvent. As the above-mentioned substrate, a woven or non-woven fabric of organic fibers or glass fibers is generally used as a laminated board so far. The amount of varnish impregnated into the base material is preferably such that the weight ratio of the resin solid content in the prepreg is 35% by weight or more. Generally, the dielectric constant of the base material is larger than that of the resin, and therefore, when the content of the resin solid content in the prepreg is small, the dielectric constant of the laminate obtained using this prepreg becomes large. For example, E
When the resin prepreg using the glass cloth has a resin solid content of 37% by weight or more, a dielectric constant of 3.7 or less can be achieved, and the prepreg using the D glass cloth as the base material is 45% by weight.
With the above resin solid content, a dielectric constant of 3.2 or less can be achieved. In the present invention, the heating and drying conditions for preparing the prepreg vary depending on the type and amount of the reaction catalyst used, but the desired gelling time of the resin composition contained in the prepreg can be obtained. The heating and drying conditions may be set as described above.
【００２２】本発明においては、上記のプリプレグを用
いて積層板を作製することができる。詳しく説明する
と、本発明のプリプレグを一枚又は複数枚重ね、さらに
その上下の両面もしくは片面に銅箔等の金属箔を重ねた
ものを加熱加圧成形することにより、積層一体化された
両面金属箔張もしくは片面金属箔張積層板を作製するこ
とができる。この積層板の金属箔をエッチング加工等し
て回路形成することによってプリント配線板を得ること
ができ、さらには、このプリント配線板を内層プリント
配線板として、本発明のプリプレグを間に介して複数枚
重ねると共に、その最外層に金属箔を重ねたものを加熱
加圧成形することによって、多層プリント配線板を作製
することができる。なお、成形条件は、本発明の樹脂組
成物の原料の配合比率により異なり、特に限定するもの
ではないが、一般的には温度１７０〜２３０℃、圧力１
０〜５０kg/cm2の条件で適切な時間、加熱加圧するのが
好ましく、さらに、加熱加圧終了後に圧力開放化で２０
０〜２５０℃の温度で再加熱すると樹脂固形分の硬化を
より促進させることができる。In the present invention, a laminated board can be produced using the above prepreg. More specifically, one or a plurality of prepregs of the present invention are stacked, and further, a metal foil such as a copper foil is stacked on both upper and lower surfaces or one surface of the prepreg, which is heat-pressed to form a laminated and integrated double-sided metal. Foil-clad or single-sided metal foil-clad laminates can be made. A printed wiring board can be obtained by forming a circuit by etching a metal foil of this laminated board, and further, this printed wiring board is used as an inner layer printed wiring board, and a plurality of prepregs of the present invention are interposed therebetween. A multilayer printed wiring board can be produced by stacking a plurality of sheets and stacking a metal foil on the outermost layer thereof and performing heat-press molding. The molding conditions vary depending on the compounding ratio of the raw material of the resin composition of the present invention and are not particularly limited, but generally a temperature of 170 to 230 ° C., a pressure of 1
It is preferable to heat and pressurize under a condition of 0 to 50 kg / cm 2 for an appropriate time.
Reheating at a temperature of 0 to 250 ° C. can further accelerate the curing of the resin solid content.
【００２３】[0023]
実施例１ 下記の（化６）に示す２．２−ビス（４−シアネートフ
ェニル）プロパンのモノマー及びプレポリマーの混合物
（***バイエル社製：品番ＫＵ−６５７３）を多官能性
シアネートエステルとして、下記の（化７）に示すＮ−
フェニルマレイミド（三井東圧化学社製：品名ＰＭＩ）
をモノマレイミド化合物として重量比率で８：２となる
ように配合し、これを溶媒のトリクロロエチレンに樹脂
固形分の濃度が７０重量％となるように溶解させ、さら
にこれに反応触媒としてナフテン酸コバルトをシアネー
トエステルに対して重量で６０ｐｐｍ添加し、攪拌して
均一に混合させてワニスを得た。そして、このワニスを
Ｅガラスクロス（旭シュエーベル社製：品番２１６Ｌ）
に含浸し、温度１５０℃、２分間の条件で加熱乾燥して
溶媒を除去し、樹脂含有量が３５重量％のプリプレグを
得た。さらに、このプリプレグを４枚重ね、その上下両
側に厚さ７０μの両面粗化銅箔を重ねて、温度１７０
℃、圧力４０kg/cm2、９０分間の成形条件で積層一体化
し、その後、圧力開放化で電気オーブンにて温度２３０
℃、２時間の条件で再加熱して、厚さ０．４ｍｍの内層
プリント配線板用の両面銅張積層板を得た。Example 1 A mixture of a 2.2-bis (4-cyanatephenyl) propane monomer and a prepolymer (Chemical Formula 6) shown below (product number KU-6573, manufactured by Bayer GmbH, West Germany) was used as a polyfunctional cyanate ester. N- shown in (Chemical Formula 7)
Phenylmaleimide (Mitsui Toatsu Chemicals, Inc .: product name PMI)
As a monomaleimide compound in a weight ratio of 8: 2, and this was dissolved in trichloroethylene as a solvent so that the concentration of the resin solid content was 70% by weight, and cobalt naphthenate as a reaction catalyst was further added thereto. A varnish was obtained by adding 60 ppm by weight to the cyanate ester, stirring and mixing uniformly. Then, use this varnish with E glass cloth (manufactured by Asahi Schwebel: product number 216L).
And the solvent was removed by heating and drying at a temperature of 150 ° C. for 2 minutes to obtain a prepreg having a resin content of 35% by weight. Furthermore, four sheets of this prepreg are stacked, and double-sided roughened copper foil with a thickness of 70 μ is stacked on the upper and lower sides thereof, and the temperature is set to 170
Laminated and integrated under molding conditions of 90 ° C, pressure of 40 kg / cm 2 for 90 minutes, and then release the pressure to a temperature of 230 in an electric oven.
It was reheated under the condition of 2 ° C. for 2 hours to obtain a double-sided copper-clad laminate for an inner layer printed wiring board having a thickness of 0.4 mm.
【００２４】[0024]
【化６】 [Chemical 6]
【００２５】[0025]
【化７】 [Chemical 7]
【００２６】実施例２ 上記の（化６）に示す２．２−ビス（４−シアネートフ
ェニル）プロパンのモノマー及びプレポリマーの混合物
（***バイエル社製：品番ＫＵ−６５７３）を多官能性
シアネートエステルとして、下記の（化８）に示すＮ−
（２．４．６−トリブロモフェニル）マレイミド（三井
東圧化学社製：品名ＴＢ−ＰＭＩ）をモノマレイミド化
合物として重量比率で７：３となるように配合し、これ
を溶媒のトリクロロエチレンに樹脂固形分の濃度が７０
重量％となるように溶解させ、さらにこれに反応触媒と
してナフテン酸コバルトをシアネートエステルに対して
重量で６０ｐｐｍ添加し、攪拌して均一に混合させてワ
ニスを得た。以下、実施例１と同様にしてプリプレグを
作成し、さらにこのプリプレグを用いて積層一体成形し
た後、再加熱して、厚さ０．４ｍｍの内層プリント配線
板用の両面銅張積層板を得た。Example 2 A mixture of 2.2-bis (4-cyanatephenyl) propane monomer and a prepolymer (Chemical Formula 6) (product number KU-6573 manufactured by Bayer, Germany) was used as a polyfunctional cyanate ester. As shown in (Chemical Formula 8) below.
(2. 4.6-Tribromophenyl) maleimide (manufactured by Mitsui Toatsu Chemicals, Inc .: product name TB-PMI) was blended as a monomaleimide compound in a weight ratio of 7: 3, and this was mixed with a solvent of trichloroethylene as a resin. Solids concentration is 70
It was dissolved so as to have a weight percentage of 60 ppm by weight of cobalt naphthenate as a reaction catalyst with respect to the cyanate ester as a reaction catalyst, and the mixture was stirred and uniformly mixed to obtain a varnish. Hereinafter, a prepreg was prepared in the same manner as in Example 1, further laminated and integrally molded using this prepreg, and then reheated to obtain a double-sided copper clad laminate for an inner layer printed wiring board having a thickness of 0.4 mm. It was
【００２７】[0027]
【化８】 [Chemical 8]
【００２８】実施例３ 上記の（化６）に示す２．２−ビス（４−シアネートフ
ェニル）プロパンのモノマー及びプレポリマーの混合物
（***バイエル社製：品番ＫＵ−６５７３）を多官能性
シアネートエステルとして、上記の（化８）に示すＮ−
（２．４．６−トリブロモフェニル）マレイミド（三井
東圧化学社製：品名ＴＢ−ＰＭＩ）をモノマレイミド化
合物として重量比率で７：３となるように配合し、さら
に下記の（化９）に示すＰＰＯ（ＧＥジャパン社製：品
番ＰＸ９７０１）を樹脂固形分全体に対して５重量％配
合して、これらを溶媒のトリクロロエチレンに樹脂固形
分の濃度が７０重量％となるように溶解させ、さらにこ
れに反応触媒としてナフテン酸コバルトをシアネートエ
ステルに対して重量で６０ｐｐｍ添加し、攪拌して均一
に混合してワニスを得た。以下、実施例１と同様にして
プリプレグを作製し、さらにこのプリプレグを用いて積
層一体成形した後、再加熱して、厚さ０．４ｍｍの内層
プリント配線板用の両面銅張積層板を得た。Example 3 A mixture of 2.2-bis (4-cyanatephenyl) propane monomer and prepolymer (Chemical Formula 6) (product number KU-6573 manufactured by Bayer Germany) was used as a polyfunctional cyanate ester. As N- shown in (Chemical Formula 8) above
(2. 4.6-Tribromophenyl) maleimide (manufactured by Mitsui Toatsu Chemicals, Inc .: product name TB-PMI) was blended as a monomaleimide compound in a weight ratio of 7: 3, and further the following (Chemical Formula 9) 5% by weight of PPO (manufactured by GE Japan: product number PX9701) with respect to the entire resin solid content is dissolved in trichlorethylene as a solvent so that the concentration of the resin solid content is 70% by weight, and 60 ppm by weight of cobalt naphthenate as a reaction catalyst was added to the cyanate ester as a reaction catalyst, and the mixture was stirred and uniformly mixed to obtain a varnish. Hereinafter, a prepreg was produced in the same manner as in Example 1, further laminated and integrally molded using this prepreg, and then reheated to obtain a double-sided copper-clad laminate for an inner layer printed wiring board having a thickness of 0.4 mm. It was
【００２９】[0029]
【化９】 [Chemical 9]
【００３０】比較例１ 上記の（化６）に示す２．２−ビス（４−シアネートフ
ェニル）プロパンのモノマー及びプレポリマーの混合物
（***バイエル社製：品番ＫＵ−６５７３）を単独で溶
媒のトリクロロエチレンに樹脂固形分の濃度が７０重量
％となるように溶解させ、さらにこれに反応触媒として
ナフテン酸コバルトをシアネートエステルに対して重量
で６０ｐｐｍ添加し、攪拌して均一に混合してワニスを
得た。以下、実施例１と同様にしてプリプレグを作製
し、さらにこのプリプレグを用いて積層一体成形した
後、再加熱して、厚さ０．４ｍｍの内層プリント配線板
用の両面銅張積層板を得た。Comparative Example 1 A mixture of 2.2-bis (4-cyanatephenyl) propane monomer and a prepolymer (Chemical Formula 6) (product number KU-6573 manufactured by Bayer, West Germany) alone was used as a solvent trichlorethylene. Was dissolved so that the concentration of the resin solid content was 70% by weight, and 60 ppm by weight of cobalt naphthenate as a reaction catalyst was added to the cyanate ester as a reaction catalyst, and the mixture was stirred and uniformly mixed to obtain a varnish. . Hereinafter, a prepreg was produced in the same manner as in Example 1, further laminated and integrally molded using this prepreg, and then reheated to obtain a double-sided copper-clad laminate for an inner layer printed wiring board having a thickness of 0.4 mm. It was
【００３１】（性能測定）上記のようにして得られた両
面銅張積層板について、誘電率（１ＭＨｚ）、誘電正接
（１ＭＨｚ）、吸湿率、加熱後のクラック発生数、難燃
性、面内の板厚偏差の測定を行った。下記の表中の誘電
率及び誘電正接については、ＪＩＳ−Ｃ−６４８１に準
拠して測定した。吸湿率は、上記積層板を５０×５０ｍ
ｍの正方形に切り取ったものを試料とし、まず、この試
料を乾燥器で温度１００℃、１時間処理して水分を除去
した後の重量を測定し、続いて温度８５℃、湿度８５％
で９６時間、吸湿処理した後の重量を測定して、その重
量差をこの試料の吸湿処理前の重量で除した値の百分率
で表した。また、加熱後のクラック発生数については、
上記吸湿率の測定に用いた試料を温度２５０℃、１４日
間処理した後、板表面に発生したクラックの数で評価し
た。難燃性については、ＵＬ規格に準拠して測定した。
面内板厚偏差については、上記積層板の５００×６００
ｍｍの長方形に切り取った板の厚みを、板の周辺におい
て８点、板の中心１点、の計９点測定し、その厚みのバ
ラツキを標準偏差σn-1 （ｍｍ）で評価した。以上の測
定結果を表１に示した。(Performance measurement) Regarding the double-sided copper clad laminate obtained as described above, dielectric constant (1 MHz), dielectric loss tangent (1 MHz), moisture absorption rate, number of cracks generated after heating, flame retardancy, in-plane The plate thickness deviation was measured. The dielectric constant and dielectric loss tangent in the table below were measured according to JIS-C-6481. The moisture absorption rate is 50 x 50 m for the above laminated plate.
A sample cut out into a square of m was used as a sample. First, the sample was treated with a dryer at a temperature of 100 ° C. for 1 hour to remove water, and then the weight was measured, followed by a temperature of 85 ° C. and a humidity of 85%.
After 96 hours of moisture absorption treatment, the weight was measured, and the difference in weight was divided by the weight of the sample before moisture absorption treatment, and expressed as a percentage. Regarding the number of cracks generated after heating,
The sample used for measuring the moisture absorption rate was treated at a temperature of 250 ° C. for 14 days, and then evaluated by the number of cracks generated on the plate surface. The flame retardancy was measured according to UL standard.
Regarding the in-plane plate thickness deviation, 500 × 600 of the above laminated plate
The thickness of the plate cut into a rectangle of 8 mm was measured at 8 points around the plate and 1 point at the center of the plate for a total of 9 points, and the variation in the thickness was evaluated by the standard deviation σ n-1 (mm). The above measurement results are shown in Table 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】表１の結果から判るように、実施例１〜３
と比較例１を比べると、実施例１〜３に係る積層板は吸
湿率が半分以下に低減しており、加熱後のクラック発生
も認められなかった。また、誘電率及び誘電正接につい
ては、ＪＩＳ−Ｃ−６４８１における常態でほぼ同等の
値であり、吸水処理後では、その値の劣化が抑制され
た。さらに、ハロゲン化された有機基を有するモノマレ
イミド化合物を含有した実施例２及び３では、ＵＬ規格
で９４Ｖ−０レベルの難燃性が付与され、ＰＰＯを含有
した実施例３では、面内の板厚精度がＰＰＯを含有しな
い他例に比較して３〜４倍向上した。As can be seen from the results in Table 1, Examples 1 to 3
Comparing Comparative Example 1 with Comparative Example 1, the laminated sheets according to Examples 1 to 3 had a moisture absorption rate reduced to less than half, and no cracking was observed after heating. In addition, the dielectric constant and the dielectric loss tangent are almost the same value in the normal state according to JIS-C-6481, and the deterioration of the values was suppressed after the water absorption treatment. Furthermore, in Examples 2 and 3 containing a monomaleimide compound having a halogenated organic group, flame retardancy of 94V-0 level was given by UL standard, and in Example 3 containing PPO, in-plane The plate thickness accuracy was improved 3 to 4 times as compared with other examples containing no PPO.
【００３４】[0034]
【発明の効果】本発明の熱硬化性樹脂組成物は、多官能
性シアネートエステルの他にモノマレイミド化合物及び
シアネートエステルの反応触媒を含有しているので、こ
の熱硬化性樹脂組成物を用いると、シアネートエステル
樹脂の硬化物が本来有する誘電特性を保持しながら欠点
である吸湿性が低減した積層板を製造することができ
る。さらに上記の成分にＰＰＯを加えた熱硬化性樹脂組
成物を用いると、上述の効果に加えて面内の板厚精度が
向上した積層板を製造することができる。そして、本発
明の製造方法に係るプリプレグは、これらの熱硬化性樹
脂組成物を基材に含浸し、加熱乾燥して半硬化させて得
たものなので、吸湿性が低減し、さらには、面内の板厚
精度が向上した積層板を製造することができる。さら
に、本発明の製造方法に係る積層板は、このプリプレグ
を積層成形して得たものなので、誘電特性の吸湿による
劣化を抑制し、同時に吸湿した水の加熱時の気化膨張に
よるクラックの発生を防止することができる。The thermosetting resin composition of the present invention contains a monomaleimide compound and a reaction catalyst for a cyanate ester in addition to the polyfunctional cyanate ester. Therefore, when the thermosetting resin composition is used, It is possible to manufacture a laminate having reduced hygroscopicity, which is a drawback, while maintaining the original dielectric properties of the cured product of the cyanate ester resin. Further, by using the thermosetting resin composition in which PPO is added to the above components, it is possible to manufacture a laminated plate having an improved in-plane plate thickness accuracy in addition to the above effects. Then, the prepreg according to the production method of the present invention is obtained by impregnating these thermosetting resin compositions into a substrate, heating and drying and semi-curing, so that the hygroscopicity is reduced, and further, the surface It is possible to manufacture a laminated plate having an improved plate thickness accuracy. Further, since the laminated plate according to the production method of the present invention is obtained by laminating and molding this prepreg, it suppresses the deterioration of the dielectric property due to moisture absorption, and at the same time, the occurrence of cracks due to vaporization expansion during the heating of moisture absorbed water. Can be prevented.
Claims (4)
イミド化合物、及び上記多官能性シアネートエステルの
反応触媒を含有して成ることを特徴とする熱硬化性樹脂
組成物。1. A thermosetting resin composition comprising a polyfunctional cyanate ester, a monomaleimide compound, and a reaction catalyst for the polyfunctional cyanate ester.
イミド化合物、ポリフェニレンオキサイド、及び上記多
官能性シアネートエステルの反応触媒を含有して成るこ
とを特徴とする熱硬化性樹脂組成物。2. A thermosetting resin composition comprising a polyfunctional cyanate ester, a monomaleimide compound, a polyphenylene oxide, and a reaction catalyst for the polyfunctional cyanate ester.
物を基材に含浸し、加熱乾燥して半硬化させるプリプレ
グの製造方法。3. A method for producing a prepreg in which a base material is impregnated with the thermosetting resin composition according to claim 1 and heat-dried to be semi-cured.
る積層板の製造方法。4. A method for manufacturing a laminated plate, which comprises laminating and molding the prepreg according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5141019A JP2842152B2 (en) | 1993-06-11 | 1993-06-11 | Thermosetting resin composition, method for producing prepreg, and method for producing laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5141019A JP2842152B2 (en) | 1993-06-11 | 1993-06-11 | Thermosetting resin composition, method for producing prepreg, and method for producing laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06345864A true JPH06345864A (en) | 1994-12-20 |
| JP2842152B2 JP2842152B2 (en) | 1998-12-24 |
Family
ID=15282312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5141019A Expired - Fee Related JP2842152B2 (en) | 1993-06-11 | 1993-06-11 | Thermosetting resin composition, method for producing prepreg, and method for producing laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2842152B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006022309A (en) * | 2004-06-09 | 2006-01-26 | Mitsubishi Gas Chem Co Inc | Curable resin composition |
| US7071266B2 (en) * | 2003-01-17 | 2006-07-04 | Mitsubishi Gas Chemical Company, Inc. | Curable resin composition and cured product thereof |
| CN104448821A (en) * | 2013-09-17 | 2015-03-25 | 深圳光启创新技术有限公司 | Resin material for prepreg, prepreg, preparation method thereof, and meta-material substrate and meta-material containing the prepreg |
| CN111511839A (en) * | 2017-12-22 | 2020-08-07 | 帝人株式会社 | Thermosetting resin composition |
| CN113337115A (en) * | 2021-06-18 | 2021-09-03 | 西北工业大学 | High-toughness high-heat-resistance cyanate ester resin system and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107234851B (en) * | 2017-06-23 | 2019-03-26 | 重庆德凯实业股份有限公司 | High-frequency high-speed method for manufacturing cover clad laminate and its copper-clad plate |
-
1993
- 1993-06-11 JP JP5141019A patent/JP2842152B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7071266B2 (en) * | 2003-01-17 | 2006-07-04 | Mitsubishi Gas Chemical Company, Inc. | Curable resin composition and cured product thereof |
| JP2006022309A (en) * | 2004-06-09 | 2006-01-26 | Mitsubishi Gas Chem Co Inc | Curable resin composition |
| CN104448821A (en) * | 2013-09-17 | 2015-03-25 | 深圳光启创新技术有限公司 | Resin material for prepreg, prepreg, preparation method thereof, and meta-material substrate and meta-material containing the prepreg |
| CN111511839A (en) * | 2017-12-22 | 2020-08-07 | 帝人株式会社 | Thermosetting resin composition |
| CN111511839B (en) * | 2017-12-22 | 2023-03-31 | 帝人株式会社 | Thermosetting resin composition |
| CN113337115A (en) * | 2021-06-18 | 2021-09-03 | 西北工业大学 | High-toughness high-heat-resistance cyanate ester resin system and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2842152B2 (en) | 1998-12-24 |
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