JP3937676B2 - Epoxy resin composition, and prepreg and printed wiring board using the same - Google Patents
Epoxy resin composition, and prepreg and printed wiring board using the same Download PDFInfo
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- JP3937676B2 JP3937676B2 JP2000077459A JP2000077459A JP3937676B2 JP 3937676 B2 JP3937676 B2 JP 3937676B2 JP 2000077459 A JP2000077459 A JP 2000077459A JP 2000077459 A JP2000077459 A JP 2000077459A JP 3937676 B2 JP3937676 B2 JP 3937676B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、実質的にハロゲンを含まずに難燃性を付与したエポキシ樹脂組成物に関する。このエポキシ樹脂組成物は、ガラス繊維の織布や不織布、有機繊維の織布や不織布などシート状繊維基材に含浸してプリプレグを製造するのに適する。さらに、前記プリプレグを加熱加圧成形した絶縁層は、プリント配線板の絶縁層に適する。
【０００２】
【従来の技術】
プリント配線板の樹脂絶縁層は、エポキシ樹脂等の熱硬化性樹脂組成物をシート状繊維基材に保持させてなるもので、熱硬化性樹脂組成物をシート状繊維基材に含浸乾燥したプリプレグの層を加熱加圧成形して形成する。実質的にハロゲンを配合することなく、樹脂絶縁層に難燃性を付与するために、前記樹脂組成物に水酸化アルミニウムを配合することが広く行なわれている。水酸化アルミニウムは加熱されると熱分解して水を生成し、この水の消火作用によって樹脂絶縁層を燃えにくくしている。
【０００３】
【発明が解決しようとする課題】
水酸化アルミニウムは２５０℃程度で熱分解して水を生成する。難燃性付与のために水酸化アルミニウムを添加した樹脂絶縁層の耐熱性は、熱硬化性樹脂の耐熱性をいくら高くしておいても、水酸化アルミニウムの熱分解温度によって決定されてしまう。そして、樹脂の燃焼温度に達する前に、水酸化アルミニウムが熱分解して水を生成すると、樹脂の燃焼時にはもはや消火作用は発揮されない。
【０００４】
本発明が解決しようとする課題は、難燃性付与のためにエポキシ樹脂組成物に配合した水酸化アルミニウムの熱分解温度を高めることである。また、このようなエポキシ樹脂組成物を用いたプリプレグ、当該プレプレグを加熱加圧成形してなる絶縁層を備えたプリント配線板を提供することである。
【０００５】
【課題を解決するための手段】
上記課題を解決するために、本発明に係るエポキシ樹脂組成物は、ハロゲンを実質的に含まず、樹脂固形分１００質量部に対して、充填材として下記の式（１）により表される化合物を２０〜２００質量部含有し、硬化剤がノボラック樹脂であることを特徴とする。
【０００６】
【化２】
【０００７】
上記の式（１）により表される化合物は、水酸化アルミニウムと比較して熱分解温度が約１００℃高いことが知られている（特開平６−２２００６７）。充填材として式（１）の化合物を含有したエポキシ樹脂組成物をシート状繊維基材に含浸乾燥してプリプレグを製造し、当該プリプレグの層を加熱加圧成形した絶縁層は、充填材として水酸化アルミニウムを含有したエポキシ樹脂組成物をシート状繊維基材に含浸乾燥してプリプレグを製造し、当該プリプレグの層を加熱加圧成形した絶縁層と比較して、良好な耐熱性を保持することになる。
式（１）の化合物の配合量は、樹脂固形分１００質量部に対して、２０〜２００質量部が適当である。配合量が２０質量部に満たないと十分な難燃効果を得られず、配合量が２００質量部を越えると絶縁層や積層板の機械的強度が低下してしまうため好ましくない。
また式（１）の化合物が有する難燃効果を充分に発揮するためには、エポキシ樹脂硬化物の熱分解温度が前記化合物の熱分解温度より高くなるようエポキシ樹脂および硬化剤を選定する必要がある。耐熱性が高いエポキシ樹脂硬化物を得るためには、硬化剤としてノボラック樹脂を使用することが有効である。硬化剤として酸無水物、ジシアンジアミド等を使用した場合、得られたエポキシ樹脂硬化物の熱分解温度が式（１）の化合物の熱分解温度より低くなるため、充分な難燃効果が得られない。
【０００８】
【発明の実施の形態】
本発明に係るエポキシ樹脂組成物は、エポキシ樹脂の種類を特に限定するものではないが、ビスフェノールＡ型エポキシ樹脂（二官能エポキシ樹脂）、三官能エポキシ樹脂、フェノールノボラック型エポキシ樹脂やクレゾールノボラック型エポキシ樹脂さらにはビスフェノールＡノボラック型エポキシ樹脂などの多官能エポキシ樹脂を用いる。式（１）の化合物は熱分解温度が高いために、三官能エポキシ樹脂や多官能エポキシ樹脂など耐熱性の高いエポキシ樹脂を選択することにより、当該樹脂の耐熱性を遺憾なく発揮させることができる。また、硬化剤として選択するノボラック樹脂は、フェノールノボラック樹脂、ビスフェノールＡノボラック樹脂、あるいはトリアジン環を含有するフェノールノボラック樹脂等である。
【０００９】
このエポキシ樹脂組成物をガラス繊維や有機繊維で構成されたシート状繊維基材（織布や不織布）に含浸乾燥してプリプレグとする。当該プリプレグの層を加熱加圧成形した絶縁層を片面プリント配線板、両面プリント配線板、さらには多層プリント配線板の絶縁層とする。また、当該プリプレグの層を加熱加圧成形して絶縁板としたり、成形に際して金属箔を一体化したプリント配線板製造用の金属箔張り積層板とする。
【００１０】
【実施例】
実施例１
密閉可能な容器に蓚酸の１０質量％水溶液１６００ｇと水酸化アルミニウム１００ｇを投入し、攪拌した後、容器を密閉し、１６５℃で４時間加熱し、室温まで冷却する。その後、容器中の沈殿物をろ過、洗浄し、１１０℃で２０時間乾燥することにより、式（１）の化合物を得た。
充填材として式（１）の化合物２０質量部、クレゾールノボラック型エポキシ樹脂（エポキシ当量２１０）６７質量部、フェノールノボラック樹脂（水酸基当量１０５）３３質量部、２−エチル４−メチルイミダゾール０．１質量部を混合攪拌してエポキシ樹脂組成物を調製した。
上記エポキシ樹脂組成物を０．２mm厚のガラス繊維織布に含浸乾燥してプリプレグを製造し、このプリプレグ４枚の両面に１８μｍ厚銅箔を載置して加熱加圧成形により一体化し、０．８mm厚の両面銅張り積層板とした。
【００１１】
実施例２
式（１）の化合物を５０質量部配合するほかは実施例１と同様にして両面銅張り積層板とした。
【００１２】
実施例３
式（１）の化合物を１００質量部配合するほかは実施例１と同様にして両面銅張り積層板とした。
【００１３】
実施例４
式（１）の化合物を２００質量部配合するほかは実施例１と同様にして両面銅張り積層板とした。
【００１４】
比較例１
式（１）の化合物を１０質量部配合するほかは実施例１と同様にして両面銅張り積層板とした。
【００１５】
比較例２
充填材として式（１）の化合物の代わりに水酸化アルミニウムを２００質量部配合するほかは実施例１と同様にして両面銅張り積層板とした。
【００１６】
従来例１
クレゾールノボラック型エポキシ樹脂（エポキシ当量２１０）５５質量部、テトラブロモビスフェノールＡ（水酸基当量２７２）３０質量部、フェノールノボラック樹脂（水酸基当量１０５）１５質量部、２−エチル４−メチルイミダゾール０．１質量部を混合攪拌してエポキシ樹脂組成物を調製した。
上記エポキシ樹脂組成物を０．２mm厚のガラス繊維織布に含浸乾燥してプリプレグを製造し、このプリプレグ４枚の両面に１８μｍ厚銅箔を載置して加熱加圧成形により一体化し、０．８mm厚の両面銅張り積層板とした。
【００１７】
上記各例の銅張り積層板について、半田耐熱性、難燃性を評価した結果を表１に示した。表中に示した各特性は、次のように評価した。
半田耐熱性は、ＪＩＳ Ｃ−６４８１に準拠し、試料を所定温度の半田槽に浮かべ、試料に膨れが発生するまでの時間を測定した。
難燃性は、ＵＬ−９４試験法に基づき残炎時間を測定した。
【００１８】
【表１】
【発明の効果】
上述のように、本発明に係る樹脂組成物は、水酸化アルミニウムを配合した場合より半田耐熱性が高いだけでなく、難燃性に優れた絶縁層を形成するので有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin composition imparted with flame retardancy substantially free of halogen. This epoxy resin composition is suitable for producing a prepreg by impregnating a sheet-like fiber base material such as a woven or non-woven fabric of glass fiber or a woven or non-woven fabric of organic fiber. Furthermore, the insulating layer obtained by heating and pressing the prepreg is suitable for an insulating layer of a printed wiring board.
[0002]
[Prior art]
The resin insulation layer of the printed wiring board is obtained by holding a thermosetting resin composition such as an epoxy resin on a sheet-like fiber base material, and a prepreg obtained by impregnating and drying the thermosetting resin composition on the sheet-like fiber base material. These layers are formed by heating and pressing. In order to impart flame retardancy to the resin insulation layer without substantially adding halogen, it is widely practiced to add aluminum hydroxide to the resin composition. When aluminum hydroxide is heated, it is thermally decomposed to produce water, and the water-extinguishing action makes the resin insulating layer difficult to burn.
[0003]
[Problems to be solved by the invention]
Aluminum hydroxide is thermally decomposed at about 250 ° C. to produce water. The heat resistance of the resin insulation layer to which aluminum hydroxide has been added for imparting flame retardancy is determined by the thermal decomposition temperature of aluminum hydroxide, no matter how high the heat resistance of the thermosetting resin is. If the aluminum hydroxide is thermally decomposed to generate water before reaching the combustion temperature of the resin, the fire extinguishing action is no longer exhibited during the combustion of the resin.
[0004]
The problem to be solved by the present invention is to increase the thermal decomposition temperature of aluminum hydroxide blended in an epoxy resin composition for imparting flame retardancy. Moreover, it is providing the printed wiring board provided with the prepreg using such an epoxy resin composition, and the insulating layer formed by heat-press-molding the said prepreg.
[0005]
[Means for Solving the Problems]
In order to solve the above problems, the epoxy resin composition according to the present invention is substantially free of halogen, and is a compound represented by the following formula (1) as a filler with respect to 100 parts by mass of resin solid content. 20 to 200 parts by mass, and the curing agent is a novolac resin.
[0006]
[Chemical 2]
[0007]
The compound represented by the above formula (1) is known to have a thermal decomposition temperature about 100 ° C. higher than that of aluminum hydroxide (JP-A-6-220067). An insulating layer formed by impregnating and drying an epoxy resin composition containing the compound of formula (1) as a filler into a sheet-like fiber base material to produce a prepreg, and heating and press-molding the layer of the prepreg is water as a filler. Impregnating and drying an epoxy resin composition containing aluminum oxide into a sheet-like fiber substrate to produce a prepreg, and maintaining good heat resistance as compared with an insulating layer obtained by heating and pressing the prepreg layer. become.
The amount of the compound of formula (1) is suitably 20 to 200 parts by mass with respect to 100 parts by mass of the resin solid content. If the blending amount is less than 20 parts by mass, a sufficient flame retardant effect cannot be obtained, and if the blending amount exceeds 200 parts by mass, the mechanical strength of the insulating layer and the laminate is lowered, which is not preferable.
In order to fully exhibit the flame retardant effect of the compound of formula (1), it is necessary to select an epoxy resin and a curing agent so that the thermal decomposition temperature of the cured epoxy resin is higher than the thermal decomposition temperature of the compound. is there. In order to obtain a cured epoxy resin having high heat resistance, it is effective to use a novolac resin as a curing agent. When an acid anhydride, dicyandiamide, or the like is used as a curing agent, the thermal decomposition temperature of the obtained epoxy resin cured product is lower than the thermal decomposition temperature of the compound of the formula (1), so that a sufficient flame retardant effect cannot be obtained. .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The epoxy resin composition according to the present invention is not particularly limited in the type of epoxy resin, but bisphenol A type epoxy resin (bifunctional epoxy resin), trifunctional epoxy resin, phenol novolac type epoxy resin and cresol novolac type epoxy. Further, a polyfunctional epoxy resin such as a bisphenol A novolac type epoxy resin is used. Since the compound of formula (1) has a high thermal decomposition temperature, the heat resistance of the resin can be exerted regretfully by selecting a highly heat-resistant epoxy resin such as a trifunctional epoxy resin or a polyfunctional epoxy resin. . The novolak resin selected as the curing agent is a phenol novolak resin, a bisphenol A novolak resin, a phenol novolak resin containing a triazine ring, or the like.
[0009]
This epoxy resin composition is impregnated and dried into a sheet-like fiber base material (woven fabric or non-woven fabric) made of glass fiber or organic fiber to obtain a prepreg. The insulating layer obtained by heat-pressing the prepreg layer is used as a single-sided printed wiring board, a double-sided printed wiring board, or an insulating layer of a multilayer printed wiring board. Further, the prepreg layer is formed by heating and pressing to form an insulating plate, or a metal foil-clad laminate for manufacturing a printed wiring board in which a metal foil is integrated during forming.
[0010]
【Example】
Example 1
In a sealable container, 1600 g of a 10% by mass aqueous solution of oxalic acid and 100 g of aluminum hydroxide are added and stirred. The container is then sealed, heated at 165 ° C. for 4 hours, and cooled to room temperature. Then, the compound in Formula (1) was obtained by filtering and wash | cleaning the deposit in a container, and drying at 110 degreeC for 20 hours.
As a filler, 20 parts by mass of the compound of the formula (1), 67 parts by mass of a cresol novolac-type epoxy resin (epoxy equivalent 210), 33 parts by mass of a phenol novolac resin (hydroxyl equivalent 105), 0.1 mass of 2-ethyl 4-methylimidazole Parts were mixed and stirred to prepare an epoxy resin composition.
A prepreg is produced by impregnating and drying a 0.2 mm thick glass fiber woven fabric with the above epoxy resin composition, 18 μm thick copper foil is placed on both sides of the four prepregs, and integrated by heat and pressure molding. .8 mm thick double-sided copper-clad laminate.
[0011]
Example 2
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except that 50 parts by mass of the compound of formula (1) was blended.
[0012]
Example 3
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except that 100 parts by mass of the compound of formula (1) was blended.
[0013]
Example 4
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except that 200 parts by mass of the compound of formula (1) was blended.
[0014]
Comparative Example 1
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except that 10 parts by mass of the compound of formula (1) was blended.
[0015]
Comparative Example 2
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except that 200 parts by mass of aluminum hydroxide was blended in place of the compound of formula (1) as the filler.
[0016]
Conventional Example 1
55 parts by mass of cresol novolac type epoxy resin (epoxy equivalent 210), 30 parts by mass of tetrabromobisphenol A (hydroxyl equivalent 272), 15 parts by mass of phenol novolac resin (hydroxyl equivalent 105), 0.1 mass of 2-ethyl 4-methylimidazole Parts were mixed and stirred to prepare an epoxy resin composition.
A prepreg is produced by impregnating and drying a 0.2 mm thick glass fiber woven fabric with the above epoxy resin composition, 18 μm thick copper foil is placed on both sides of the four prepregs, and integrated by heat and pressure molding. .8 mm thick double-sided copper-clad laminate.
[0017]
Table 1 shows the results of evaluating the solder heat resistance and flame retardancy of the copper-clad laminates of the above examples. Each characteristic shown in the table was evaluated as follows.
The solder heat resistance was measured in accordance with JIS C-6481, by measuring the time until the sample was floated in a solder bath at a predetermined temperature and the sample was swollen.
For flame retardancy, the afterflame time was measured based on the UL-94 test method.
[0018]
[Table 1]
【The invention's effect】
As described above, the resin composition according to the present invention is useful because it forms not only higher solder heat resistance than when aluminum hydroxide is blended, but also an insulating layer having excellent flame retardancy.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000077459A JP3937676B2 (en) | 2000-03-21 | 2000-03-21 | Epoxy resin composition, and prepreg and printed wiring board using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000077459A JP3937676B2 (en) | 2000-03-21 | 2000-03-21 | Epoxy resin composition, and prepreg and printed wiring board using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001261938A JP2001261938A (en) | 2001-09-26 |
| JP3937676B2 true JP3937676B2 (en) | 2007-06-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000077459A Expired - Fee Related JP3937676B2 (en) | 2000-03-21 | 2000-03-21 | Epoxy resin composition, and prepreg and printed wiring board using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3937676B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662173B (en) * | 2020-06-03 | 2023-03-24 | 中铝山东有限公司 | Aluminum hydroxy oxalate and preparation method thereof, and high-purity aluminum oxide |
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2000
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2001261938A (en) | 2001-09-26 |
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