JP4778833B2 - Laminate substrate and prepreg, and laminate - Google Patents
Laminate substrate and prepreg, and laminate Download PDFInfo
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- JP4778833B2 JP4778833B2 JP2006140096A JP2006140096A JP4778833B2 JP 4778833 B2 JP4778833 B2 JP 4778833B2 JP 2006140096 A JP2006140096 A JP 2006140096A JP 2006140096 A JP2006140096 A JP 2006140096A JP 4778833 B2 JP4778833 B2 JP 4778833B2
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- 239000000758 substrate Substances 0.000 title claims description 18
- 229920003235 aromatic polyamide Polymers 0.000 claims description 51
- 239000004760 aramid Substances 0.000 claims description 50
- 239000000835 fiber Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 18
- -1 polyparaphenylene terephthalamide Polymers 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 22
- 229920000561 Twaron Polymers 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 239000004762 twaron Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000271 Kevlar® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Description
本発明は、耐熱性及び電気絶縁性に優れ、電気回路用積層物に好適に使用できる芳香族ポリアミド繊維紙に関するものであり、さらに詳しくは、高強力且つ低吸湿、更に、耐熱寸法安定性に優れ、電気回路用積層板に好適に使用できる積層板用基材及びそれからなるプリプレグ、並びに積層板に関するものである。 The present invention relates to an aromatic polyamide fiber paper that is excellent in heat resistance and electrical insulation and can be suitably used for laminates for electric circuits. More specifically, the present invention relates to high strength and low moisture absorption, and further to heat resistant dimensional stability. The present invention relates to a laminate base material that can be suitably used for an electrical circuit laminate, a prepreg comprising the same, and a laminate.
電気回路板用積層物に使用される基材には、耐熱性や耐熱寸法安定性、耐湿寸法安定性、電気絶縁性、耐変形性(捩れ、反り、波打ちなどを生じ難いこと)などの特性が要求される。また携帯電話、ノート型パソコンなどの小型電子機器用においては、高密度化が必要となるため、前記の特性と合わせて、軽量性、薄葉化などの諸特性が要求される。芳香族ポリアミド繊維紙は、他素材からなる紙基材に比べて、耐熱性、電気絶縁性、耐熱寸法安定性、軽量性などの点で優れているため、前記の諸特性が要求される電気回路板用積層物の基材にもよく活用されるようになってきた。 Base materials used in laminates for electric circuit boards have characteristics such as heat resistance, heat-resistant dimensional stability, moisture-resistant dimensional stability, electrical insulation, and deformation resistance (not easily torsion, warpage, undulation, etc.) Is required. In addition, for small electronic devices such as mobile phones and laptop computers, it is necessary to increase the density. Therefore, various characteristics such as lightness and thinning are required in addition to the above characteristics. Aromatic polyamide fiber paper is superior to other paper base materials in terms of heat resistance, electrical insulation, heat-resistant dimensional stability, lightness, etc. It has come to be used well as a base material for laminates for circuit boards.
例えば、ポリパラフェニレンテレフタルアミド短繊維(デュポン(株)製「ケブラー」)やコポリパラフェニレン・3,4’−オキシジフェニレン・テレフタルアミド短繊維(帝人テクノプロダクツ(株)製「テクノーラ」)と有機系樹脂バインダーからなる芳香族ポリアミド繊維紙(特開平1−92233号公報)や芳香族ポリアミド紙の製造方法(特開平2−47392号公報)などが提案されている。 For example, polyparaphenylene terephthalamide short fiber ("Kevlar" manufactured by DuPont) and copolyparaphenylene 3,4'-oxydiphenylene terephthalamide short fiber ("Technora" manufactured by Teijin Techno Products Co., Ltd.) Aromatic polyamide fiber paper made of an organic resin binder (Japanese Patent Laid-Open No. 1-92233) and a method for producing aromatic polyamide paper (Japanese Patent Laid-Open No. 2-47392) have been proposed.
しかし、該特許記載の芳香族ポリアミド繊維紙は、湿式抄紙製造工程中で湿紙が切断しやすく、薄葉化に限界がある。また、バインダー樹脂の耐熱性が芳香族ポリアミドに比べて劣る為、電気回路用積層物の製造工程、特に鉛フリーハンダをフローする工程でバインダー樹脂の劣化による機械的物性低下、又吸湿等により性能が低下するという問題点があった。 However, the aromatic polyamide fiber paper described in the patent has a limitation in thinning because the wet paper is easily cut during the wet papermaking process. In addition, since the heat resistance of the binder resin is inferior to that of aromatic polyamide, the performance of the laminate for electrical circuits, especially the flow of lead-free solder, decreases mechanical properties due to deterioration of the binder resin, and absorbs moisture. There has been a problem of lowering.
また、ポリパラフェニレンテレフタルアミド短繊維とポリメタフェニレンイソフタルアミドフィブリッドからなるパラアラミド紙(特公平5−65640号公報など)も提案されている。ポリメタフェニレンイソフタルアミドフィブリッドを使用することにより湿式抄紙製造工程中で湿紙が切断されにくくなる効果はあるものの紙強度はさほど上がらず、より薄葉化するには限界があり、更にポリメタフェニレンイソフタルアミドフィブリッドは耐熱性がパラ型芳香族ポリアミドに比べて劣る為、電気回路用積層物としたときに、特に昨今の携帯機器の高性能化で要求される、大容量の情報伝達によって発生する積層板の温度上昇に耐えられず、また吸湿が大きいため、温度上昇の際の寸法変化が大きくなり、好ましくない。 In addition, para-aramid paper (such as Japanese Patent Publication No. 5-65640) composed of polyparaphenylene terephthalamide short fibers and polymetaphenylene isophthalamide fibrids has been proposed. The use of polymetaphenylene isophthalamide fibrids has the effect of making the wet paper difficult to cut in the wet papermaking process, but the paper strength does not increase so much, and there is a limit to making it thinner. Because isophthalamide fibrids are inferior in heat resistance to para-type aromatic polyamides, when they are used as laminates for electrical circuits, they are generated due to the transmission of large volumes of information, which is required especially for the recent high performance of portable devices. Since the laminated board cannot withstand the temperature rise and the moisture absorption is large, the dimensional change at the time of temperature rise becomes large, which is not preferable.
本発明の目的は、芳香族ポリアミド繊維を用いた積層板用基材の問題であった、耐熱性、耐熱寸法安定性、及び薄葉化の問題を解決し、高密度化が可能で、かつ大容量の情報伝達による積層板の温度上昇にも耐えうる積層板用基材を得ることにある。 The object of the present invention is to solve the problems of heat resistance, heat-resistant dimensional stability, and thinning, which have been problems of laminated base materials using aromatic polyamide fibers, and can be increased in density and large. An object of the present invention is to obtain a laminated board substrate that can withstand the temperature rise of the laminated board due to transmission of capacity information.
本発明者らは、前記課題を解決するために鋭意検討した結果、積層板用基材を芳香族ポリアミド繊維と芳香族ポリアミドパルプと必要に応じて有機系樹脂バインダーから構成し、そのうち芳香族ポリアミドパルプとして、パラ型芳香族ポリアミドからなり、且つ、該パラ型芳香族ポリアミドパルプの乾燥収縮率が10%以上であるパルプを用いたとき、耐熱寸法安定性に優れ、且つ薄葉化可能な積層板用基材が得られることを見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have constituted a laminated board base material from aromatic polyamide fibers, an aromatic polyamide pulp and, if necessary, an organic resin binder, of which an aromatic polyamide Laminate which is excellent in heat-resistant dimensional stability and can be thinned when a pulp made of para-type aromatic polyamide and having a drying shrinkage of 10% or more is used as the pulp. The present inventors have found that a base material for use can be obtained, and have reached the present invention.
すなわち、本発明によれば、パラ型芳香族ポリアミド短繊維と芳香族ポリアミドパルプを主成分とする積層板用基材であって、該芳香族ポリアミドパルプが、乾燥収縮率が10%以上であるポリパラフェニレンテレフタルアミドからなり、且つ該ポリパラフェニレンテレフタルアミドパルプが積層板用基材全重量に対して10%以上、30%以下含まれることを特徴とする積層板用基材が提供される。 That is, according to the present invention, there is provided a laminate base material mainly composed of para-type aromatic polyamide short fibers and aromatic polyamide pulp, and the aromatic polyamide pulp has a drying shrinkage of 10% or more. consists polyparaphenylene terephthalamide, it is and the polyparaphenylene terephthalamide pulp more than 10% of the total weight base material laminate, provides laminate base material, characterized in that contained 30% .
以上に説明した本発明の積層板用基材によれば、パラ型芳香族ポリアミドからなる乾燥収縮率の高いパルプを用いることにより、特に基材強度を向上させることができ、よってより薄葉の基材とすることができる。また、パラ型芳香族ポリアミドの高耐熱性により基材の耐熱寸法安定性も向上させることができる。したがって、該基材を用いた電気回路板用積層板は、薄葉かつ耐熱寸法安定性に優れるので、高密度化が可能で、半導体配線基板、フレキシブルプリント配線板用基材としても好適に使用できる。 According to the laminated board substrate of the present invention described above, the strength of the substrate can be particularly improved by using a pulp made of para-type aromatic polyamide and having a high drying shrinkage rate. It can be a material. Moreover, the high heat resistance of para-type aromatic polyamide can also improve the heat-resistant dimensional stability of the substrate. Therefore, the laminate for an electric circuit board using the base material is thin and excellent in heat-resistant dimensional stability, so that the density can be increased and it can be suitably used as a base material for a semiconductor wiring board or a flexible printed wiring board. .
以下、本発明について詳細に説明する。
本発明における積層板用基材は、芳香族ポリアミド短繊維と芳香族ポリアミドパルプ及び必要に応じて有機系樹脂バインダーとを主成分として形成された耐熱性繊維紙からなるものである。
Hereinafter, the present invention will be described in detail.
The base material for laminated boards in this invention consists of a heat resistant fiber paper formed by using an aromatic polyamide short fiber, an aromatic polyamide pulp and, if necessary, an organic resin binder as main components.
また、本発明においてプリプレグとは、不織布(紙)等の基材に熱硬化性樹脂を含浸させ乾燥した1枚のシートを言い、更に、積層板とは、複数枚のプリプレグを加熱加圧成形したもの、又は、それに金属箔張りをしたものを言う。また、内層と表面層にプリント配線を有するいわゆる多層板も含む。 In the present invention, the prepreg refers to a single sheet obtained by impregnating a base material such as a nonwoven fabric (paper) with a thermosetting resin and dried, and the laminated plate refers to a plurality of prepregs formed by heating and pressing. Or the one with metal foil attached to it. Moreover, what is called a multilayer board which has a printed wiring in an inner layer and a surface layer is also included.
本発明において芳香族ポリアミドとは、ポリアミドを構成する繰り返し単位の80モル%以上(好ましくは90モル%以上)が、下記式(1)で表される芳香族ホモポリアミド、または、芳香族コポリアミドからなる短繊維である。ここでAr1、Ar2は芳香族基を表し、なかでも下記式(2)から選ばれた同一の、または、相異なる芳香族基からなるものが好ましい。但し、芳香族基の水素原子は、ハロゲン原子、低級アルキル基、フェニル基などで置換されていてもよい。 In the present invention, the aromatic polyamide is an aromatic homopolyamide or aromatic copolyamide in which 80 mol% or more (preferably 90 mol% or more) of the repeating units constituting the polyamide is represented by the following formula (1): It is the short fiber which consists of. Here, Ar 1 and Ar 2 represent an aromatic group, and among them, those composed of the same or different aromatic groups selected from the following formula (2) are preferable. However, the hydrogen atom of the aromatic group may be substituted with a halogen atom, a lower alkyl group, a phenyl group, or the like.
このような芳香族ポリアミド繊維の製造方法や繊維特性については、例えば、英国特許第1501948号公報、米国特許第3733964号明細書、第3767756号明細書、第3869429号明細書、日本国特許の特開昭49−100322号公報、特開昭47−10863号公報、特開昭58−144152号公報、特開平4−65513号公報などに記載されており、特に耐熱性の優れたものとしてパラ型芳香族ポリアミド短繊維があげられるが、これは前記芳香族ポリアミドの延鎖結合が共軸または平行で、且つ、反対方向に向いているポリアミドからなる短繊維であり、例えば、前記Ar1、Ar2の80モル%以上がパラ配位の芳香族基であるポリアミドである。 Regarding the production method and fiber characteristics of such aromatic polyamide fibers, for example, British Patent No. 1501948, US Pat. Nos. 3,733,964, 3,767,756, 3,869,429, and Japanese Patent JP-A-49-100322, JP-A-47-10863, JP-A-58-144152, JP-A-4-65513, etc. An aromatic polyamide short fiber is mentioned, which is a short fiber made of polyamide in which the chain bond of the aromatic polyamide is coaxial or parallel and is directed in the opposite direction. For example, Ar 1 , Ar 2 is a polyamide in which 80 mol% or more of 2 is a para-coordinate aromatic group.
具体的には、ポリパラフェニレンテレフタルアミド短繊維(例えば、デュポン(株)製「ケブラー」)、コポリパラフェニレン・3,4’−オキシジフェニレン・テレフタルアミド短繊維(帝人テクノプロダクツ(株)製「テクノーラ」)等が例示され、特に後者は、不純イオンの含有量が少ないので電気絶縁性に優れているのでより好ましい。 Specifically, polyparaphenylene terephthalamide short fibers (for example, “Kevlar” manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4′-oxydiphenylene terephthalamide short fibers (manufactured by Teijin Techno Products Co., Ltd.) “Technola”) and the like are exemplified, and the latter is particularly preferable because the content of impure ions is small and the electrical insulation is excellent.
上記のパラ型芳香族ポリアミド短繊維が積層板用基材の全重量に対して占める比率は50〜98重量%であることが好ましい。より好ましくは60〜95重量%である。該比率が上記範囲を外れる場合は、得られる積層板用基材の熱寸法安定性が不良となり好ましくない。 The ratio of the para-type aromatic polyamide short fibers to the total weight of the laminate base material is preferably 50 to 98% by weight. More preferably, it is 60 to 95% by weight. When the ratio is out of the above range, the thermal dimensional stability of the obtained laminated board base material is poor, which is not preferable.
また、上記のパラ型芳香族ポリアミド短繊維の短繊維繊度は、0.11〜5.5dtexであることが好ましい。0.11dtex未満では、製糸技術の面で困難な点が多く、断糸や毛羽が発生して良好な品質の繊維を安定に生産することが困難になるだけでなく、コストも高くなるため好ましくない。一方、5.5dtexを越えると、繊維の機械的物性、特に強度低下が大きくなるため、基材の製造工程上で断紙が発生するなど困難となるためやはり好ましくない。 Moreover, it is preferable that the short fiber fineness of said para type | mold aromatic polyamide short fiber is 0.11-5.5 dtex. If it is less than 0.11 dtex, there are many difficult points in terms of the spinning technique, and it is not only difficult to stably produce fibers of good quality due to the occurrence of yarn breakage and fluff, but it is also preferable because the cost increases. Absent. On the other hand, if it exceeds 5.5 dtex, the mechanical properties of the fiber, particularly the strength, will be greatly reduced, and it will be difficult to generate a paper break in the production process of the base material.
本発明で使用する芳香族ポリアミドパルプは、ポリパラフェニレンテレフタルアミドからなり、且つ、該ポリパラフェニレンテレフタルアミドの乾燥収縮率が10%以上であるパルプを用いることを特徴とする。 Aromatic polyamide pulp used in the present invention comprises a poly-para-phenylene terephthalamide and, drying shrinkage of the polyparaphenylene terephthalamide is characterized by using a pulp of 10% or more.
ここで芳香族ポリアミドパルプとは、芳香族ポリアミドからなる微小のフィブリルを有する薄葉状、鱗片状の小片、又は、ランダムにフィブリル化した微小短繊維の総称である。該芳香族ポリアミドパルプとしては、例えば、特公昭35−11851号公報、特公昭37−5732号公報、WO2004/99476等に記載された方法により、有機系高分子重合体溶液を該高分子重合体溶液の沈澱剤と剪断力の存在する系において混合することにより製造される。本発明の乾燥収縮率が10%以上であるポリパラフェニレンテレフタルアミドパルプは、乾燥時に収縮すると共に短繊維同士を接着するバインダーの機能を持つため大量の連続生産には適しており、中でもWO2004/99476に記載されているパルプは、耐熱寸法安定性にも優れている点から最適である。 Here, the aromatic polyamide pulp is a general term for thin leaf-like or scaly pieces having fine fibrils made of aromatic polyamide, or randomly short fibrillated microfibers. Examples of the aromatic polyamide pulp, For example, Japanese Patent Publication 35-11851, JP-B-37-5732 and JP according to the method described in such as WO2004 / 99 476, the polymer weight organic polymer polymer solution It is produced by mixing in a system in the presence of a shearing force with a precipitant of a coalesced solution. The polyparaphenylene terephthalamide pulp having a drying shrinkage rate of 10% or more according to the present invention is suitable for large-scale continuous production since it has a function of a binder that shrinks during drying and bonds short fibers to each other. pulp that is described in 99476 is optimal from the point that excellent resistance to thermal dimensional stability.
本発明におけるパルプの乾燥収縮率とは、パラ型芳香族ポリアミドパルプを、タッピー抄紙機を用いて公知の湿式抄造法により100g/m2の紙を抄造し、抄造直後の湿紙シート面積と、その湿紙シートを無圧下、120℃で5時間乾燥させて得られたシートの面積から以下の式によって算出したものをいう。
(乾燥収縮率)=[(湿紙でのシート面積)−(乾燥後のシート面積)]/(湿紙でのシート面積)×100
The drying shrinkage of the pulp in the present invention is a para-type aromatic polyamide pulp, a 100 g / m 2 paper is made by a known wet paper making method using a tappy paper machine, the wet paper sheet area immediately after paper making, The wet paper sheet is calculated from the area of a sheet obtained by drying the wet paper sheet at 120 ° C. for 5 hours under no pressure by the following formula.
(Dry shrinkage) = [(sheet area with wet paper) − (sheet area after drying)] / (sheet area with wet paper) × 100
パラ型芳香族ポリアミドパルプの乾燥収縮率は10%以上、好ましくは15%以上である。このような乾燥収縮率の高いパルプを用いることにより、湿紙の乾燥時に細かいフィブリルが乾燥とともに収縮し他の繊維と絡み合い、短繊維同士を強固に繋ぐと同時に接着し、その結果基材強度が上がり、薄葉化しても連続生産に耐えうる高強度な基材を得ることができる。一方、乾燥収縮率が10%未満の場合は、基材強度が上がらず薄葉化した場合に連続生産に耐えうる強度を基材に持たせることができないため好ましくない。 The drying shrinkage of the para-type aromatic polyamide pulp is 10% or more, preferably 15% or more. By using such a pulp having a high drying shrinkage rate, fine fibrils shrink with drying when wet paper is dried and entangle with other fibers, firmly connecting short fibers together, and as a result, the substrate strength is increased. It is possible to obtain a high-strength base material that can withstand continuous production even if it rises and thins. On the other hand, a drying shrinkage ratio of less than 10% is not preferable because the base material cannot be given strength sufficient to withstand continuous production when the base material strength does not increase and thinned.
また、該パルプの本発明中の積層板用基材に占める比率は、10〜30重量%である。その配合は、基材の目付け、積層板としたときの寸法安定性など、目的とする電気回路用積層物の要求特性を見極めながら決定すればよい。何れにせよ、該パルプの混合比率が30重量%を超えると、得られる積層板用基材の嵩密度が高くなりすぎ、配合ワニスの含浸性を阻害するようになり、好ましくない。 Further, percentage of laminate base material in the present invention the pulp is 10 to 30 wt%. The blending may be determined while ascertaining the required characteristics of the target laminate for an electric circuit, such as the basis weight of the base material and the dimensional stability when used as a laminate. In any case, if the mixing ratio of the pulp exceeds 30 % by weight, the resulting bulk density of the laminate base material becomes too high, impairing the impregnation of the blended varnish, which is not preferable.
また、前記芳香族ポリアミドパルプは、湿式抄造工程において短繊維間を結合せしめるバインダーとしての機能を有する。 Also, the aromatic polyamide pulp, that have a function as a binder allowed to coupling between the short fibers in the wet papermaking process.
以上述べた積層板用基材は、従来公知の方法により製造することができる。例えば、コポリパラフェニレン・3,4’−オキシジフェニレン・テレフタルアミド短繊維を所定の比率になるように秤量し、繊維濃度が約0.15〜0.40重量%の範囲になる様に水中に投入して均一分散させ、調整した水性スラリー中に、必要に応じて、分散剤や粘度調整剤を加えた後、長網式や丸網式等の抄紙機による湿式抄造法で湿紙を形成し、この湿紙にもし必要ならば、有機系のバインダー樹脂をスプレー方式等により所定の固形分比率の重量になるよう付与した後、乾燥して得た乾燥紙を所定の嵩密度の範囲となるように加熱加圧加工して芳香族ポリアミド繊維紙を得ることが出来る。 The laminate substrate described above can be produced by a conventionally known method. For example, copolyparaphenylene / 3,4′-oxydiphenylene / terephthalamide short fibers are weighed to a predetermined ratio, and the fiber concentration is about 0.15 to 0.40% by weight in water. After adding a dispersing agent and a viscosity adjusting agent to the adjusted aqueous slurry as necessary, the wet paper is formed by a wet paper making method using a paper machine such as a long net type or a round net type. If the wet paper is formed, if necessary, an organic binder resin is applied to the weight of a predetermined solid content ratio by a spray method or the like, and then dried to obtain a dry paper having a predetermined bulk density range. An aromatic polyamide fiber paper can be obtained by heating and pressing so that
以上に説明した本発明の芳香族ポリアミド繊維紙は、従来公知の方法(工程)で製造することができる。例えば、パラ型芳香族ポリアミド短繊維、パラ型芳香族ポリアミドパルプを、定められた所定の割合となるように秤量し、繊維濃度(パルプ含む)が約0.15〜0.40重量%となるように水中に投入して均一分散、調整した水性スラリー中に、必要に応じて、分散剤や粘度調整剤を加えた後、長網式や丸網式等の抄紙機による湿式抄造法で湿紙を形成し、該湿紙を乾燥して得た乾燥紙を加熱加圧加工することにより、所望の目付、厚さ、耐熱寸法安定性を有する積層板用基材として得ることができる。 The aromatic polyamide fiber paper of the present invention described above can be produced by a conventionally known method (process). For example, para-type aromatic polyamide short fibers and para-type aromatic polyamide pulp are weighed to have a predetermined ratio, and the fiber concentration (including pulp) is about 0.15 to 0.40% by weight. After adding a dispersing agent and a viscosity adjusting agent to the aqueous slurry that has been uniformly dispersed and adjusted after being introduced into water as described above, the wet slurry is added by a wet papermaking method using a paper machine such as a long net type or a round net type. A dry paper obtained by forming paper and drying the wet paper can be heated and pressed to obtain a laminate base material having a desired basis weight, thickness, and heat-resistant dimensional stability.
加熱加圧加工の条件は、例えば、カレンダー機を用いて加熱加圧する場合には、直径約15〜80cmからなる1ケの硬質表面ロールと、直径約30〜100cmの表面変形可能な弾性ロールとの間で、好ましくは、直径約20〜80cmからなる2ケの硬質表面ロール同士の間で行えばよい。また、電気回路板用積層物の製造工程には240℃以上で高温熱処理する工程があるため、この熱処理温度以上の熱履歴を基材に予め与えておくと、この熱処理工程での紙の熱寸法変化や内部歪み誘発を抑制し、得られる積層物の耐熱寸法安定性や耐変形性が向上するのでより好ましい。本発明者らの検討によれば、温度:300〜400℃、線圧:1764〜3920N/cmの範囲でカレンダー加工するのが最適であり、この条件で作成された芳香族ポリアミド繊維紙は、耐熱寸法安定性に優れ、また、引張強力も優れたものが得られる。なお、該加熱加圧条件が400℃、3920N/cmを超えると、カレンダー加工中に紙切れが生じてしまうため好ましくない。 The conditions for the heat and pressure processing are, for example, when a heat and pressure is applied using a calendar machine, one hard surface roll having a diameter of about 15 to 80 cm, and a surface deformable elastic roll having a diameter of about 30 to 100 cm Between the two hard surface rolls having a diameter of about 20 to 80 cm. In addition, since there is a process of high-temperature heat treatment at 240 ° C. or higher in the manufacturing process of the laminate for electric circuit boards, if a heat history higher than this heat treatment temperature is given to the substrate in advance, the heat of the paper in this heat treatment process It is more preferable because it suppresses dimensional change and internal strain induction, and improves the heat-resistant dimensional stability and deformation resistance of the resulting laminate. According to the study by the present inventors, it is optimal to calender at a temperature of 300 to 400 ° C. and a linear pressure of 1764 to 3920 N / cm, and the aromatic polyamide fiber paper produced under these conditions is An excellent heat-resistant dimensional stability and excellent tensile strength can be obtained. If the heating and pressing conditions exceed 400 ° C. and 3920 N / cm, it is not preferable because paper breakage occurs during calendar processing.
このような加熱加圧加工処理により、本発明の芳香族ポリアミド繊維紙の嵩密度は、0.55〜0.90g/cm3、好ましくは、0.60〜0.85g/cm3の範囲内に入るように製紙工程で調整、コントロールすることが可能である。 By such a heating and pressing process, the bulk density of the aromatic polyamide fiber paper of the present invention is in the range of 0.55 to 0.90 g / cm 3 , preferably 0.60 to 0.85 g / cm 3 . It is possible to adjust and control in the papermaking process so as to enter.
以下、実施例により本発明をさらに詳細に説明する。なお、実施例で用いた試験片の作成方法、及びその評価方法は下記の通りである。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the preparation method of the test piece used in the Example and its evaluation method are as follows.
(1)パラ型芳香族ポリアミドパルプの作製
ポリパラフェニレンテレフタルアミド(帝人トワロン社製「トワロン」)を用い、WO2004/99476の手法に準じて作製した(トワロンパルプ1とする)。このパルプを前記の式により計算した乾燥収縮率は29.4%であった。
(1) Preparation of para-type aromatic polyamide pulp Polyparaphenylene terephthalamide (“Twaron” manufactured by Teijin Twaron Co., Ltd.) was used and manufactured according to the method of WO 2004/99476 (referred to as Twaron pulp 1). The drying shrinkage ratio of this pulp calculated by the above formula was 29.4%.
(2)積層板用基材の作製
パラ型芳香族ポリアミド短繊維、及び前記(1)で作成されたパラ型芳香族ポリアミドパルプを用いて水中に分散させ、これに0.02%濃度になるように分散剤(松本油脂(株)製「YM−80」)を添加して、繊維(パルプ含む)濃度が0.15重量%であるスラリーを作成した。
次に、タッピー式角型抄紙機を用い、該スラリーを使用して抄紙し、軽く加圧脱水後に、該混抄紙を温度:110℃で乾燥させ、さらに、1対の金属ロールを有するカレンダー装置で温度:200℃〜350℃、線圧力:1960N/cm(200kg/cm)、カレンダー速度:4m/分の条件でカレンダ―処理を行い坪量15g/m2の芳香族ポリアミド繊維紙を得た。
(2) Production of base material for laminate plate Para type aromatic polyamide short fibers and the para type aromatic polyamide pulp prepared in the above (1) are dispersed in water, resulting in a concentration of 0.02%. Thus, a dispersing agent (“YM-80” manufactured by Matsumoto Yushi Co., Ltd.) was added to prepare a slurry having a fiber (including pulp) concentration of 0.15 wt%.
Next, using a tappy type square paper machine, paper is made using the slurry, and after light pressure dehydration, the mixed paper is dried at a temperature of 110 ° C., and a calender device having a pair of metal rolls Temperature: 200 ° C. to 350 ° C., linear pressure: 1960 N / cm (200 kg / cm), calendar speed: 4 m / min, and calendering was performed to obtain an aromatic polyamide fiber paper having a basis weight of 15 g / m 2 . .
(3)紙の坪量
JIS P 8124に準拠して測定した。
(3) Basis weight of paper Measured according to JIS P 8124.
(4)紙の厚さ及び嵩密度
JIS P 8118に準拠して測定した。
(4) Paper thickness and bulk density Measured in accordance with JIS P 8118.
(5)裂断長
JIS P 8113に準拠して測定した。
(5) Breaking length Measured according to JIS P8113.
(6)紙の熱寸法変化率
高精度二次元座標測定機(ムトウ工業(株)製)を用い、長さ250mm、幅50mmの試料の長さ方向について、熱処理前と温度300℃で5分間熱処理した後の長さを測定し、下記計算式により熱寸法変化率を算出した。なお、測定用の試料は、連続紙の長さ方向と幅方向から採取して測定し、その平均値で比較判定した。
熱寸法変化率(%)={(|熱処理前の長さ−熱処理後の長さ|)
/熱処理前の長さ}×100
(6) Thermal dimensional change rate of paper Using a high-precision two-dimensional coordinate measuring machine (manufactured by Mutou Industry Co., Ltd.), in the length direction of a sample having a length of 250 mm and a width of 50 mm, before heat treatment and at a temperature of 300 ° C. for 5 minutes. The length after heat treatment was measured, and the thermal dimensional change rate was calculated by the following formula. In addition, the sample for a measurement was extract | collected and measured from the length direction of the continuous paper, and the width direction, and compared and determined by the average value.
Thermal dimensional change rate (%) = {(| Length before heat treatment−Length after heat treatment |)
/ Length before heat treatment} × 100
(7)積層板の変形量
高純度のブロム化ビスフェノールA型エポキシ樹脂及びオルソクレゾールノボラック型エポキシ樹脂に硬化剤としてジシアンジアミド、硬化促進剤として2−エチル−4メチルイミダゾールを配合してなるエポキシ樹脂組成物をメチルエチルケトンとメチルセルソルブの混合溶液に溶解して得た配合ワニスを芳香族ポリアミド繊維基材に含浸させた後、温度110〜120℃で5〜10分間乾燥して、樹脂分の体積含有率が55%であるBステージのプリプレグ紙を作成した。
該プリプレグ紙を厚さ:12μの銅箔の両側に積層し、さらに、その外側に同一の銅箔を積層し、ホットプレスにより、減圧下で170℃×40kg/cm×50分間の条件でプレスを行い、樹脂を硬化せしめて電気回路板用積層板を作成し、更に温度200℃の熱風乾燥機内で約20分間硬化処理を行った。
この電気回路板用積層板を150mm角に裁断し、当該積層物の端部から20mmの幅で両面の銅箔を枠状に残して、中央部の110mm角相当部を全部エッチングにより銅箔を取り除いて評価用のサンプルを作製する。
この部分エッチングされた電気回路用積層物を300℃で10分間熱処理した際の中央部分を起点とした最大変形量を測定し、変形量とする。
(7) Deformation amount of laminated board Epoxy resin composition comprising dicyandiamide as curing agent and 2-ethyl-4methylimidazole as curing accelerator in high purity brominated bisphenol A type epoxy resin and orthocresol novolac type epoxy resin After impregnating the blended varnish obtained by dissolving the product in a mixed solution of methyl ethyl ketone and methyl cellosolve into the aromatic polyamide fiber base material, it is dried at a temperature of 110 to 120 ° C. for 5 to 10 minutes to contain a volume of resin content A B-stage prepreg paper having a rate of 55% was prepared.
The prepreg paper is laminated on both sides of a copper foil having a thickness of 12 μm, and the same copper foil is further laminated on the outside thereof. The hot press is pressed under reduced pressure at 170 ° C. × 40 kg / cm × 50 minutes. Then, the resin was cured to produce a laminated board for an electric circuit board, and further subjected to a curing treatment in a hot air dryer at a temperature of 200 ° C. for about 20 minutes.
This laminated board for electric circuit boards is cut into a 150 mm square, the copper foil on both sides is left in a frame shape with a width of 20 mm from the end of the laminate, and the copper foil is removed by etching the 110 mm square equivalent part of the central part. Remove and make a sample for evaluation.
The maximum deformation amount starting from the central portion when the partially etched electrical circuit laminate is heat-treated at 300 ° C. for 10 minutes is determined as the deformation amount.
[実施例1〜3、比較例1]
芳香族ポリアミド短繊維として、コポリパラフェニレン・3,4’−オキシジフェニレン・テレフタルアミド短繊維(帝人テクノプロダクツ(株)製「テクノーラ」)及び前記(1)記載のトワロンパルプ1を、表1に示した比率となるように配合し、前記(2)の方法を用いて、芳香族ポリアミドからなる積層板用基材を作製した。この基材について前記(3)〜(7)の測定法にて評価した諸特性は、表2に示すとおりである。
[Examples 1 to 3, Comparative Example 1]
As aromatic polyamide short fibers, copolyparaphenylene • 3,4′-oxydiphenylene / terephthalamide short fibers (“Technola” manufactured by Teijin Techno Products Co., Ltd.) and Twaron pulp 1 described in the above (1) are shown in Table 1. The base material for laminated boards which consists of an aromatic polyamide was produced using the method of said (2), mix | blending so that it might become the ratio shown in (4). Table 2 shows various properties of the substrate evaluated by the measurement methods (3) to (7).
[実施例4]
実施例1において、芳香族ポリアミド短繊維として、ポリパラフェニレンテレフタルアミド短繊維(帝人トワロン社製「トワロン」)を用いた以外は実施例1と同様に実施し、積層板用基材を作製した。この基材について前記(3)〜(7)の測定法にて評価した諸特性は、表2に示すとおりであった。
[Example 4 ]
In Example 1, it carried out similarly to Example 1 except having used the polyparaphenylene terephthalamide short fiber ("Twaron" by Teijin Twaron Co., Ltd.) as an aromatic polyamide short fiber, and produced the base material for laminated boards. . Various properties of this substrate evaluated by the measuring methods (3) to (7) were as shown in Table 2.
[比較例2]
実施例1において、前記(1)記載のトワロンパルプ1を用いる代わりに、ポリメタフェニレンイソフタルアミド(帝人テクノプロダクツ(株)製「コーネックス」)からなる重合体溶液を、沈澱剤と剪断力の存在する系において混合することにより作製したパルプを用いた。このパルプを前記の式により計算した乾燥収縮率は20.5%であった。このパルプを用いた以外は実施例1と同様に実施し、積層板用基材を作製した。この基材について前記(3)〜(7)の測定法にて評価した諸特性は、表2に示すとおりであった。
[Comparative Example 2]
In Example 1, instead of using the Twaron pulp 1 described in the above (1), a polymer solution composed of polymetaphenylene isophthalamide (“Conex” manufactured by Teijin Techno Products Co., Ltd.) is used. Pulp made by mixing in an existing system was used. The drying shrinkage percentage of this pulp calculated by the above formula was 20.5%. Except having used this pulp, it implemented similarly to Example 1 and produced the base material for laminated boards. Various properties of this substrate evaluated by the measuring methods (3) to (7) were as shown in Table 2.
[比較例3]
実施例1において、前記(1)記載のトワロンパルプ1を用いる代わりに、ポリパラフェニレンテレフタルアミド短繊維に機械的剪断力を与えてランダムにフィブリル化させたパルプ(帝人トワロン社製「トワロン1094」)を用いた。このパルプを前記の式により計算した乾燥収縮率は4.0%であった。このパルプを用いた以外は実施例1と同様に実施し、積層板用基材を作製した。この基材について前記(3)〜(7)の測定法にて評価した諸特性は、表2に示すとおりであった。
[Comparative Example 3]
In Example 1, instead of using the Twaron pulp 1 described in the above (1), a pulp obtained by randomly fibrillating polyparaphenylene terephthalamide short fibers by applying mechanical shearing force (“Twaron 1094” manufactured by Teijin Twaron) ) Was used. The drying shrinkage percentage of this pulp calculated by the above formula was 4.0%. Except having used this pulp, it implemented similarly to Example 1 and produced the base material for laminated boards. Various properties of this substrate evaluated by the measuring methods (3) to (7) were as shown in Table 2.
[比較例4]
実施例4において、前記(1)記載のトワロンパルプ1を用いず、代わりに、抄紙時にビスフェノールAエピクロルヒドリン型水分散性エポキシ樹脂バインダー(大日本化学工業(株)製)の水希釈液を、該樹脂の固形分付着量が20重量%になるようにスプレーした以外は実施例4と同様に実施し、積層板用基材を作製した。この基材について前記(3)〜(7)の測定法にて評価した諸特性は、表2に示すとおりであった。
[Comparative Example 4]
In Example 4, instead of using the Twaron pulp 1 described in the above (1), instead of using a water dilution of a bisphenol A epichlorohydrin type water-dispersible epoxy resin binder (manufactured by Dainippon Chemical Co., Ltd.) A substrate for laminates was produced in the same manner as in Example 4 except that the resin was sprayed so that the solid content adhered amount was 20% by weight. Various properties of this substrate evaluated by the measuring methods (3) to (7) were as shown in Table 2.
本発明の積層板用基材を用いた電気回路板用積層板は、薄葉かつ耐熱寸法安定性に優れるので、高密度化が可能となり、半導体配線基板、フレキシブルプリント配線板用基材として好適に使用できる。 The laminated board for an electric circuit board using the laminated board substrate of the present invention is thin and excellent in heat-resistant dimensional stability, so that it can be densified and is suitable as a substrate for semiconductor wiring boards and flexible printed wiring boards. Can be used.
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