JP2010024315A5 - - Google Patents
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- JP2010024315A5 JP2010024315A5 JP2008185897A JP2008185897A JP2010024315A5 JP 2010024315 A5 JP2010024315 A5 JP 2010024315A5 JP 2008185897 A JP2008185897 A JP 2008185897A JP 2008185897 A JP2008185897 A JP 2008185897A JP 2010024315 A5 JP2010024315 A5 JP 2010024315A5
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- JP
- Japan
- Prior art keywords
- printed wiring
- varnish
- wiring board
- polymerizable monomer
- acid group
- Prior art date
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- 239000002966 varnish Substances 0.000 claims description 32
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000007870 radical polymerization initiator Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- -1 3-methoxybutyl Chemical group 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000002313 adhesive film Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N Tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N Triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- FHNCCAGEZMNIHZ-UHFFFAOYSA-N 3,4,5,5a,6,7,8,9-octahydro-2H-1,2-benzodiazepine Chemical compound N1CCCC2CCCCC2=N1 FHNCCAGEZMNIHZ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N Diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N ethylene glycol monomethyl ether Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N methoxyethyl Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、優れた流動性を発現し、その硬化物において耐熱性に優れるために、プリント回路基板、ビルドアップ用接着フィルムに好適に用いる事が出来るエポキシ樹脂組成物、及びその硬化物に関する。 The present invention relates to an epoxy resin composition that can be suitably used for a printed circuit board and an adhesive film for build-up, and a cured product thereof, because it exhibits excellent fluidity and has excellent heat resistance in the cured product.
即ち、本発明は、エポキシ当量１５０〜５００ｇ／ｅｑ．のビスフェノール型エポキシ樹脂（Ａ）、酸基含有ラジカル重合性単量体（Ｂ）、及びラジカル重合開始剤（Ｃ）を必須成分とすることを特徴とするプリント配線基板用ワニスに関する。 That is, the present invention provides an epoxy equivalent of 150 to 500 g / eq. It is related with the varnish for printed wiring boards characterized by using the bisphenol-type epoxy resin (A), the acid group-containing radical polymerizable monomer (B), and the radical polymerization initiator (C) as essential components.
本発明は、更に、前記プリント配線基板用ワニスをイン・サイチュー反応させることにより得られる硬化物に関する。 The present invention further relates to a cured product obtained by reacting the varnish for a printed wiring board in situ.
本発明は、更に、前記プリント配線基板用ワニスをイン・サイチュー反応させることを特徴とする硬化物の製造方法に関する。 The present invention further relates to a method for producing a cured product, wherein the varnish for a printed wiring board is reacted in situ.
本発明は、更に、上記プリント配線基板用ワニスを繊維基材に含浸してなるプリプレグに関する。 The present invention further relates to a prepreg obtained by impregnating a fiber base material with the varnish for a printed wiring board .
本発明は、更に、前記プリプレグからなるプリント配線基板用積層板に関する。 The present invention further relates to a laminate for a printed wiring board comprising the prepreg.
本発明によれば、常温液状の組成物でありながら、かつ、硬化物の耐熱性に優れた性能を発現するプリント配線基板用ワニスを提供できる。特に、本発明の組成物は常温で優れた流動性を有する為に、プリント配線基板のプリプレグ製造時における繊維状基材への含浸性が良好であると共に、有機溶剤を使用しないか、或いは、使用量を低減できるため成形時における乾燥工程が不要乃至簡素化できるため、形成物の生産性が飛躍的に高まる。 ADVANTAGE OF THE INVENTION According to this invention, although it is a normal temperature liquid composition, the varnish for printed wiring boards which expresses the performance excellent in the heat resistance of hardened | cured material can be provided. In particular, since the composition of the present invention has excellent fluidity at normal temperature, the impregnation property to the fibrous base material at the time of manufacturing the prepreg of the printed wiring board is good, and an organic solvent is not used, or Since the amount used can be reduced, the drying process at the time of molding can be eliminated or simplified, and the productivity of the formed product can be dramatically increased.
以下、本発明を詳細に説明する。
本発明のプリント配線基板用ワニスは、前記した通り、エポキシ当量１５０〜１０００ｇ／ｅｑ．のビスフェノール型エポキシ樹脂（Ａ）、酸基含有ラジカル重合性単量体（Ｂ）、及びラジカル重合開始剤（Ｃ）を必須成分とするものであり、これを一度に反応させること、即ち、エポキシ基と酸基との反応と、ラジカル重合性基の重合反応とを特に反応工程として区別することなく両反応を同時乃至連続的に行うことを特徴としている。このようにイン・サイチュー反応により硬化させることで、硬化前においては流動性が著しく高くなる一方で、硬化物における耐熱性が飛躍的に向上させることができる。この点につき更に敷衍すれば、本発明におけるイン・サイチュー反応で得られる硬化物は、該ビスフェノール型エポキシ樹脂（Ａ）と酸基含有ラジカル重合性単量体（Ｂ）とを予め反応させてビニルエステル化したのち、これをラジカル重合させる場合に比べて、耐熱性を一層高めることができるのであり、その結果、硬化前においては優れた流動性を発現すると共に、硬化後においては従来にない耐熱性を発現するものとなる。
Hereinafter, the present invention will be described in detail.
As described above, the varnish for a printed wiring board of the present invention has an epoxy equivalent of 150 to 1000 g / eq. Bisphenol type epoxy resin (A), acid group-containing radical polymerizable monomer (B), and radical polymerization initiator (C) as essential components, and reacting them at once, that is, epoxy It is characterized in that both reactions are carried out simultaneously or continuously without distinguishing the reaction between the group and the acid group and the polymerization reaction of the radical polymerizable group as reaction steps. By curing by an in-situ reaction in this way, the fluidity is significantly increased before curing, while the heat resistance of the cured product can be dramatically improved. If this point is further spread, the cured product obtained by the in-situ reaction in the present invention is obtained by reacting the bisphenol type epoxy resin (A) with the acid group-containing radical polymerizable monomer (B) in advance. After esterification, heat resistance can be further improved compared to radical polymerization of this, and as a result, it exhibits excellent fluidity before curing and unprecedented heat resistance after curing. It expresses sex.
本発明のプリント配線基板用ワニスは、更に、硬化促進剤を適宜併用することもできる。前記硬化促進剤としては種々のものが使用できるが、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。特に光半導体封止材料用途として使用する場合には、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルフォスフィン、第３級アミンでは１，８−ジアザビシクロ−［５．４．０］−ウンデセン（ＤＢＵ）が好ましい。 The varnish for a printed wiring board of the present invention can further use a curing accelerator as appropriate. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as an optical semiconductor sealing material application, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., phosphorous compounds are triphenylphosphine, and tertiary amines are 1,8- Diazabicyclo- [5.4.0] -undecene (DBU) is preferred.
本発明のプリント配線基板用ワニスは、用途に応じて適度な柔軟性や強度などの機能性を硬化物に付与でき、かつ、ワニスの更なる低粘度化が可能となる点から、前記した（Ｂ）成分の他のラジカル重合性単量体（Ｄ）を併用することが好ましい。ここで使用し得るラジカル重合性単量体は、例えば、スチレン、メチルスチレン、ハロゲン化スチレン、ジビニルベンゼン、以下に代表される(メタ)アクリル酸エステル類が挙げられる。
本発明に使用できる単官能（メタ）アクリレートとしては例えば、メチル、エチル、プロピル、ブチル、３−メトキシブチル、アミル、イソアミル、２−エチルヘキシル、オクチル、イソオクチル、ノニル、イソノニル、デシル、イソデシル、ドデシル、トリデシル、ヘキサデシル、オクタデシル、ステアリル、イソステアリル、シクロヘキシル、ベンジル、メトキシエチル、ブトキシエチル、フェノキシエチル、ノニルフェノキシエチル、グリシジル、ジメチルアミノエチル、ジエチルアミノエチル、イソボルニル、ジシクロペンタニル、ジシクロペンテニル、ジシクロペンテニロキシエチル等の置換基を有する（メタ）アクリレート等が挙げられる。
The varnish for a printed wiring board of the present invention has been described above in terms of being able to impart functionalities such as appropriate flexibility and strength to the cured product depending on the application, and further reducing the viscosity of the varnish. It is preferable to use other radically polymerizable monomer (D) in combination with component B). Examples of the radical polymerizable monomer that can be used here include styrene, methylstyrene, halogenated styrene, divinylbenzene, and (meth) acrylic acid esters represented by the following.
Examples of the monofunctional (meth) acrylate that can be used in the present invention include methyl, ethyl, propyl, butyl, 3-methoxybutyl, amyl, isoamyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, Tridecyl, hexadecyl, octadecyl, stearyl, isostearyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclo (Meth) acrylate etc. which have substituents, such as pentenyloxyethyl, are mentioned.
また、本発明のプリント配線基板用ワニスは、上記各成分に加え、酸化防止剤を配合することが加熱時の酸化劣化を防止でき、透明性に優れた硬化物が得られる点で好ましい。 Moreover, the varnish for printed wiring boards of this invention is preferable at the point which can prevent the oxidation deterioration at the time of a heating and to obtain the hardened | cured material excellent in transparency in addition to said each component.
以上詳述した本発明のプリント配線基板用ワニスは、更に硬化物に難燃性を付与する観点から難燃剤を併用できる。ここで用いる難燃剤としては、ポリ臭素化ジフェニルエーテル、ポリ臭素化ビフェニル、テトラブロモビスフェノールＡ、テトラブロモビスフェノールＡ型エポキシ樹脂等のハロゲン系難燃剤、及び非ハロゲン系難燃剤が挙げられる。これらのなかでも特に近年のノンハロゲンの要求が高いことから非ハロゲン系難燃剤が好ましい。 The varnish for a printed wiring board of the present invention described in detail above can further use a flame retardant from the viewpoint of imparting flame retardancy to the cured product. Examples of the flame retardant used here include halogen-based flame retardants such as polybrominated diphenyl ether, polybrominated biphenyl, tetrabromobisphenol A, tetrabromobisphenol A type epoxy resin, and non-halogen flame retardants. Of these, non-halogen flame retardants are preferred because of the recent high demand for non-halogens.
本発明のプリント配線基板用ワニスは、前記した各成分を、均一に撹拌することにより、液状の組成物として容易に得ることができる。 The printed wiring board varnish of the present invention can be easily obtained as a liquid composition by uniformly stirring the above-described components.
本発明のプリント配線基板用ワニスは、前記したとおり、常温液状の組成物であり、有機溶剤無しで、或いは、極少量の使用でワニス化することができる。ここで、アセトン、メチルエチルケトン、トルエン、キシレン、メチルイソブチルケトン、酢酸エチル、エチレングリコールモノメチルエーテル、Ｎ，Ｎ−ジメチルホルムアミド、メタノール、エタノールなどが挙げられる。この有機溶剤の使用量は、組成物中１０重量％以下であることが好ましく、特に実質的に有機溶剤を使用しないことが好ましい。 As described above , the varnish for a printed wiring board of the present invention is a liquid composition at room temperature and can be varnished without using an organic solvent or by using a very small amount. Here, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, methanol, ethanol and the like can be mentioned. The amount of the organic solvent used is preferably 10% by weight or less in the composition, and it is particularly preferable that substantially no organic solvent is used.
本発明のプリント配線基板用ワニスは、上記した各成分を均一に混合することにより得られる。 The varnish for a printed wiring board of the present invention can be obtained by uniformly mixing the above-described components.
本発明のプリント配線基板用ワニスの硬化物は、以上詳述したプリント配線基板用ワニスをイン・サイチュー反応させることにより得られるものである。ここで、イン・サイチュー反応とは、前記した通り、エポキシ基と酸基との反応と、ラジカル重合性基の重合反応とを特に反応工程として区別することなく両反応を同時乃至連続的に行うものである。よって、本発明では、エポキシ樹脂用の硬化剤としてのみ機能する成分、即ち、それ自体が重合性基を持たない成分を実質的に有しないものであることが好ましい。 The hardened | cured material of the varnish for printed wiring boards of this invention is obtained by carrying out the in-situ reaction of the varnish for printed wiring boards detailed above. Here, as described above, the in-situ reaction is performed simultaneously or continuously without distinguishing the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group as reaction steps. Is. Therefore, in this invention, it is preferable that it is a thing which does not have a component which functions only as a hardening | curing agent for epoxy resins, ie, the component which does not have a polymeric group itself.
前記した硬化物は、本発明のプリント配線基板用ワニスは、常温（２５℃）で液状であり、優れた流動性を有すると共に、硬化後は極めて高い耐熱性を発現するという特徴を有することから、前記プリント配線基板用ワニスを繊維基材に含浸してなるプリプレグとして工業的に利用することが望ましく、最終的に該プリプレグを用いて成型してなる構造体として利用することが望ましい。かかる、プリプレグを用いた構造体としては、以下に詳述する各種用途のうち、プリント配線基板用積層板が挙げあれる。 Cured product described above is a printed circuit board for varnish of the present invention is a liquid at room temperature (25 ° C.), since it has the feature that has excellent fluidity, after curing express extremely high thermal resistance It is desirable to use industrially as a prepreg formed by impregnating a fiber base material with the varnish for a printed wiring board , and it is desirable to use as a structure formed by finally using the prepreg. Such as the structure using the prepreg, among various applications that will be described in detail below, rough include printed wiring board laminates.
本発明のプリント配線基板用ワニスの用途は、プリント配線基板用積層板、ビルドアップ基板用層間絶縁材料、ビルドアップ用接着フィルムが挙げられる。これらの中でも特に優れた流動性と高耐熱性を兼備するといった観点からプリント配線基板用積層板、ビルドアップ基板用層間絶縁材料、ビルドアップ用接着フィルムが好ましく、更に、線膨張係数が低く、かつ、低誘電率・低誘電正接といった性能を有する点からプリント配線基板用積層板が特に好ましい。 Applications of the varnish for a printed wiring board of the present invention include a laminated board for a printed wiring board, an interlayer insulating material for a build-up board, and an adhesive film for build-up . Among these, a laminate for printed wiring boards, an interlayer insulating material for build-up boards, and an adhesive film for build-up are preferable from the viewpoint of combining particularly excellent fluidity and high heat resistance, and furthermore, the linear expansion coefficient is low, and From the viewpoint of performance such as low dielectric constant and low dielectric loss tangent, a laminate for a printed wiring board is particularly preferable.
エポキシ当量１５０〜１０００ｇ／ｅｑ．のビスフェノール型エポキシ樹脂（Ａ）、酸基含有ラジカル重合性単量体（Ｂ）、及びラジカル重合開始剤（Ｃ）、その他必要に応じて上記した各成分を配合して得られたワニスを、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などの各種繊維基材に含浸し、用いた溶剤種に応じた加熱温度、好ましくは５０〜１７０℃で加熱することによって、硬化物であるプリプレグを得ることができる。この時用いる樹脂組成物と補強基材の質量割合としては、特に限定されないが、通常、プリプレグ中の樹脂分が２０〜６０質量％となるように調製することが好ましい。また該プリント配線基板用ワニスを用いて銅張り積層板を製造する場合は、上記のようにして得られたプリプレグを、常法により積層し、適宜銅箔を重ねて、１〜１０ＭＰａの加圧下に１７０〜２５０℃で１０分〜３時間、加熱圧着させることにより、銅張り積層板を得ることができる。 Epoxy equivalent 150-1000 g / eq. Bisphenol type epoxy resin (A), acid group-containing radical polymerizable monomer (B), radical polymerization initiator (C), and other varnish obtained by blending the above-described components as necessary, Impregnate various fiber base materials such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc., and heat at a heating temperature according to the solvent type used, preferably 50-170 ° C. Thus, a prepreg that is a cured product can be obtained. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this varnish for printed wiring boards, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.
本発明のプリント配線基板用ワニスをビルドアップ基板用層間絶縁材料として用い、ビルドアップ基板を製造するには、例えば、ゴム、フィラーなどを適宜配合した本発明のエポキシ樹脂組成物を、回路を形成した配線基板にスプレーコーティング法、カーテンコーティング法等を用いて塗布した後、硬化させる。その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、銅などの金属をめっき処理する。前記めっき方法としては、無電解めっき、電解めっき処理が好ましく、また前記粗化剤としては酸化剤、アルカリ、有機溶剤等が挙げられる。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成することにより、ビルドアップ基板を得ることができる。但し、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行う。また、銅箔上で当該樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、１７０〜２５０℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を作製することも可能である。 To produce a build-up board using the varnish for a printed wiring board of the present invention as an interlayer insulating material for a build-up board, for example, a circuit is formed by using the epoxy resin composition of the present invention appropriately blended with rubber, filler, etc. The coated wiring board is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.
本発明のプリント配線基板用ワニスからビルドアップ用接着フィルムを製造する方法は、例えば、本発明のプリント配線基板用ワニスを、支持フィルム上に塗布し樹脂組成物層を形成させて多層プリント配線板用の接着フィルムとする方法が挙げられる。 The method for producing an adhesive film for buildup from the varnish for a printed wiring board according to the present invention is, for example, a multilayer printed wiring board by applying the varnish for a printed wiring board according to the present invention on a support film to form a resin composition layer. And an adhesive film for use.
本発明のプリント配線基板用ワニスをビルドアップ用接着フィルムに用いる場合、該接着フィルムは、真空ラミネート法におけるラミネートの温度条件（通常７０℃〜１４０℃）で軟化し、回路基板のラミネートと同時に、回路基板に存在するビアホール或いはスルーホール内の樹脂充填が可能な流動性（樹脂流れ）を示すことが肝要であり、このような特性を発現するよう上記各成分を配合することが好ましい。 When the varnish for a printed wiring board of the present invention is used for an adhesive film for build-up, the adhesive film is softened under a lamination temperature condition (usually 70 ° C. to 140 ° C.) in a vacuum laminating method. It is important to show fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics.
Claims (8)
前記酸基含有ラジカル重合性単量体（Ｂ）を１〜３５質量部
となる割合で含有する請求項１記載のプリント配線基板用ワニス。 10 to 60 parts by mass of the epoxy resin (A) with respect to 100 parts by mass in total of the epoxy resin (A) and the acid group-containing radical polymerizable monomer (B),
The varnish for printed wiring boards of Claim 1 which contains the said acid group containing radically polymerizable monomer (B) in the ratio used as 1-35 mass parts.
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| EP2479200A1 (en) * | 2009-09-18 | 2012-07-25 | DIC Corporation | Resin composition for fiber-reinforced composite material, cured object obtained therefrom, fiber-reinforced composite material, fiber-reinforced molded resin, and process for producing same |
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