CN1392912A - 电气绝缘非织造织物、预浸渍体及层压板 - Google Patents

电气绝缘非织造织物、预浸渍体及层压板 Download PDF

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Publication number
CN1392912A
CN1392912A CN01802817A CN01802817A CN1392912A CN 1392912 A CN1392912 A CN 1392912A CN 01802817 A CN01802817 A CN 01802817A CN 01802817 A CN01802817 A CN 01802817A CN 1392912 A CN1392912 A CN 1392912A
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CN
China
Prior art keywords
fiber
poly
ppd
phenylenediamine
prepreg
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Granted
Application number
CN01802817A
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English (en)
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CN1232695C (zh
Inventor
车谷茂
落田学
平冈宏一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
New Oji Paper Co Ltd
Resonac Corp
Original Assignee
Shin Kobe Electric Machinery Co Ltd
Oji Paper Co Ltd
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Publication of CN1392912A publication Critical patent/CN1392912A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B29C70/885—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding with incorporated metallic wires, nets, films or plates
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
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Abstract

一种电气绝缘非织造织物具有对芳族聚酰胺纤维主要成份，该对芳族聚酰胺纤维以热固性树脂粘合剂及第二粘合剂互相粘结，该第二粘合剂是从具有软化温度220℃或更高的热塑性树脂的纤维碎块、纤维浆粕及纤条体中选出的一种粘合剂，该对芳族聚酰胺纤维是浆粕或碎块及浆粕两者，该两者碎块及浆粕的掺和质量比是0/100～95/5，而最好是50/50～90/10，聚对苯二胺对苯酰胺纤维碎块的纤维长度最好是3～6mm，在非织造织物中的热固性树脂粘合剂的含量为5～30％(质量)，而第二粘合剂的含量为5～15％(质量)。

Description

电气绝缘非织造织物、预浸渍体及层压板
技术领域
本发明涉及电气绝缘非织造织物、预浸渍体及层压板，该电气绝缘非织造织物包含的主要成分是对芳族聚酰胺纤维，该预浸渍体具有这种电气绝缘非织造织物的基底材料，该层压板含有印刷电路板及多层印刷电路板的概念。该印刷电路板及多层印刷电路板适用于表面安装无引线芯片式元件，这些元件诸如是电阻、集成电路等等。
技术背景
在诸如电阻、集成电路等电子元件安装在将被组装于电子器具中的印刷电路板上的情况下，这些芯片形式的元件通常已经通过表面安装系统安装在印刷电路板上。从电子器具的紧凑性和轻巧性及其高密集性要求的观点来看，该表面安装系统是优化的系统。伴随着印刷电路板的密集化，其间具有绝缘层的布线的连接的连接是通过主要由制孔系统制在绝缘层上的IVH(填隙通路)来完成的，该制孔系统例如是激光发射器。因此，应注意的是印刷电路板需要具有用激光发射器更易于制孔的性能。
还有，在无引线芯片式元件被表面安装在印刷电路板上的情况下，需要后者具有的热膨胀系数尽可能地与无引线芯片式元件的热膨胀系数(2～7ppm/℃)相匹配。
除此以外，希望印刷电路板具有的尺寸变化(热收缩)尽可能小，以便提高布线连接的可靠性，该布线之间设置有绝缘层。对多层印刷电路板这点特别重要。
根据这个观点，已研发了含有对芳族酰胺纤维主要成分的非织造织物作为基底材料，该对芳族酰胺纤维具有负的热膨胀系数，而该基底材料被制成印刷电路板的绝缘层。这种电气绝缘非织造织物已按如下方法制成，例如：
(1)通过造纸法中的对芳族聚酰胺纤维(聚对苯二胺-3，4，-二苯基乙醚对苯二酰胺纤维)碎块和热塑性树脂纤维碎块并同时使它们互相混合，该热塑性树脂纤维具有220℃或更高的软化温度；用热固性树脂粘合剂使它们的纤维互相粘结；并把具有220℃或更高软化温度的热性树脂纤维的碎块与对芳族聚酰胺纤维的碎块热粘结起来，生产出非织造织物(见JPA10-138381)。
(2)通过造纸法制造出对芳族聚酰胺纤维(聚对苯二胺对苯二酰胺纤维)碎块和间芳族聚酰胺纤维的纤条体并同时使它们互相混合，以及使间芳族聚酰胺纤维的纤条体与对芳族聚酰胺纤维碎块缠结而生产出非织造织物(见JPA10-160500)。
当用堆积工艺生产多层印刷电路板时，这些含有对芳族聚酰胺纤维的非织造织物被用作绝缘层的基底材料。PET(聚对苯二甲酸乙二酯)薄膜被层压在预浸渍体表面上，该预浸渍体通过以热固性树脂浸渍基底材料和加热以及使它干燥来制成，激光发射在预浸渍体的预定位置处进行制孔，并且把膏状的导电材料灌入该孔。该导电材料用作导电的印刷布线，在印刷布线之间设置有绝缘层。在PET薄膜从其内灌有膏状导电材料的预浸渍体层上去除后，铜箔被置于预浸渍体的两个表面上，在热和压力的作用下预浸渍体与铜箔构成一体，而后铜箔被插入到印刷布线，由此制成具有第一层印刷布线的印刷电路板。
在这样制成的印刷电路板上设置有铜箔，而同时具有其内灌入膏状导电材料的独立的预浸渍体被设置在印刷电路板与铜箔之间，并且它们在热及压力作用下构成一体，而后铜箔被插入到印刷布线。以这种方式该印刷布线被叠加制成多层印刷电路板(见JPA5-175650及JPA7-176846)。
根据这些现有技术，可生产出具有上及下印刷布线的多层印刷电路板；在各印刷布线之间设置有绝缘层，上及下印刷布线经过完整的IVH连接。IVH可制在导体正上方的上绝缘层中，该导体是通过使膏状导电材料固化来形成的。
对芳族聚酰胺纤维的一种聚对苯二胺-3，4’-二苯基醚对苯二酰胺纤维在纺丝时应进行牵伸以提高纤维的强度，但这种牵伸纤维在加热时易收缩。含有作为绝缘层基底材料的非织造织物(该织品具有这些纤维主要成分)的印刷电路板在软熔时具有大尺寸收缩(热收缩)。因此，表面安装在印刷电路板上的元件的连接以及其间具有绝缘层的印刷布线的连接都不利地具有不良的可靠性。
对芳族聚酰胺纤维的另一种聚对苯二胺对苯二酰胺纤维是液晶纺丝而成的以便具有较高的晶化过程并因此具有牢固的分子键。含有非织造织物(该织品具有这些纤维的主要成分)基底材料的预浸渍体或印刷电路板在通过激光发射制孔方面存在问题。聚对苯二胺对苯酰胺纤维具有高的热分解温度，并因此它在激光发射下比浸渍非织造织物的树脂具有较少的热分解及较少的基底材料扩散。于是，孔壁的表面易变得粗糙并因此灌入孔内的膏状导电材料易弄污并还具有不良的焊接性。这可能导致经隙间通过孔(IVH)的印刷电路的不良连接。
因为这些聚对苯二胺对苯酰胺纤维是液晶纺丝的，但不牵伸和纺纱，所以它们具有低的热收缩和良好的尺寸稳定性。因此，当具有造纸法制造的及通过热固性树脂粘合剂进行粘结的这些纤维的非织造织物被用作预浸渍体时，可望有较好的尺寸稳定性及较小的层压板翘曲。然而，发现并非如此，因为热作用在预浸渍体上时产生收缩使预浸渍体有弯曲倾向，并因此当热处理时，具有预浸渍体的层压板往往倾向于卷曲。
因此，本发明的目的是提供一种预浸渍体或一种层压板，它适于作印刷电路板，例如其中印刷电路板因热而生的翘曲较小，该印刷电路板具有非织造织物的绝缘层基底材料，该非织造织物含有例如聚对苯二胺对苯酰胺纤维的对芳族聚酰胺纤维主要成分。
本发明的另一个目的是提供一种预浸渍体或一种层压板，它适于作印刷电路板，其中当通过发射激光在预浸渍体上制成孔而把膏状导电材料灌入该孔时可防止该膏状导电材料产生轮廓模糊，并且其中通过降低IVH壁的粗糙度而提高了印刷电路板的布线层的连接可靠性，该IVH是利用发射激光至印刷电路板的绝缘层而制成的。
本发明的另一个目的是提供一种适于防止热收缩的预浸渍体。
本发明的还有的目的是提供一种电气绝缘非织造织物，它能使用在印刷电路板上，该印刷电路板适于完成上述目的。
本发明的公开
本发明的电气绝缘非织造织物是一种织物，它具有用粘合剂互相粘结的对芳族聚酰胺纤维主要成分以便实现本发明的目的，该纤维利用热固性树脂粘合剂及第二种粘合剂而互相粘合起来，该第二粘合剂是从纤维碎块、纤维浆粕及纤条体中选出的一种粘合剂，这些粘合剂由具有软化温度220℃或更高的热塑性树脂制成，对芳族聚酰胺纤维的特点是包含：(a)聚对苯二胺对苯酰胺纤维浆粕，或(b)聚对苯二胺对苯酰胺纤维碎块和聚对苯二胺对苯酰胺纤维浆粕两者，其纤维碎块对纤维浆粕的掺合质量比为0/100至95/5。
特别是当对芳族聚酰胺纤维主要包含如上所述的纤维浆粕形式的聚对苯二胺对苯酰胺时，由这种织品作基底材料制成的层压板可防止由热而产生的尺寸收缩。
通过对具有这种纤维作基底材料的预浸渍体进行激光发射而制孔的工作性能，可因存在聚对苯二胺对苯酰胺纤维浆粕而改善。
聚对苯二胺对苯酰胺纤维浆粕可通过把纤维碎块打浆成细小的分枝分离形状而制成。分枝分离形状的(打细)程度可用称为打浆度(csf)的打浆程度指数来表示。应理解越是打浆，打浆度就变得越小。较好打浆度为550csf或更小，而最好是1～200csf。本发明采用的打浆度是由JIS-P-8121规定的ml数值。
因为纤维碎块在其各间隙中充满了细小的分块分离的纤维浆粕，具有高的热分解温度的聚对苯二胺对苯酰胺纤维均匀地分布在纤维的整个厚度方向上。结果，当实施把激光发射到织物上的制孔操作时，孔壁内面上的容易发生升华的部分与孔壁内面上难于发生升华的部分之间没有不均匀性，而因此孔壁的最终状况变得较好。因为孔壁的粗糙度降低了，这就提高了各布线层之间连接的可靠性，该连接是通过灌入孔内的导电膏状物来完成的。相似地，提高了通过电镀孔壁完成的各布线层之间的连接的可靠性。
因为用发射激光制孔的工作更容易完成，当仅使用细纤维的纤维浆粕或纤维碎块和纤维浆粕的造纸混合物并且具有纤维浆粕对纤维碎块的高掺和比之时，细纤维在非织造织物中占有的比率变得较高并因此利用发射激光制孔的工作可容易地完成。然而，当纤维碎块及纤维浆粕的造纸混合物具有的纤维碎块对纤维浆粕的掺和质量比超过95时，用以注入纤维碎块间隙的纤维浆粕变得较短缺，而由激光发射制成的孔壁的粗糙度变大。考虑到由非织造织物作基底材料制成的绝缘层的抗热性以及孔壁的较小粗糙度，纤维碎块与纤维浆粕的掺和质量比最好是50/50～90/10。
为了防止预浸渍体的热收缩及层压板因热而生的翘曲，需要加大非织造织物的弹性模数。为预浸渍体及层压板提供较高的弹性模数可导致防止预浸渍体的热收缩和由热而产生的层压板翘曲。
在本发明中，热固性树脂粘合剂粘附在各纤维的交叉点上，由此使各纤维互相粘结，同时第二粘合剂受热熔化和粘结在对芳族聚酰胺纤维碎块上和/或与它们缠结以使它们互相粘结。两种粘合剂的混合促使非织造织物的弹性模数提高，而换句话说可以防止因受热而导致的预浸渍体及层压板的弹性模数的减缩。
第二粘合剂包含至少一种选自以下形式，即纤维碎块、纤维浆粕及具有软化温度220℃或更高的热塑性树酯的纤条体。纤维碎块是通过把直纤维切割成具有预定尺寸的能用于造纸的一种纤维而制成的，纤维浆粕是通过纤维碎块打浆而制成的，而纤条体是通过薄膜状树脂的打浆而制成的。纤维碎块可通过纤维碎块的热熔化粘结或通过热软化变形而互相缠结并用于将对芳族聚酰胺纤维互相粘结，它们是非织造织物的主要成份。纤维浆粕及纤条体本身通过使它们与对芳族聚酰胺纤维一起进行造纸生产而能互相缠结并起到使主要成分纤维互相粘结。纤维可因第二粘合剂的热软化而热熔化粘结或变形而变得更有力地互相缠结，该热软化是通过在其上加热而实现的。
本发明的预浸渍体是通过把片状的基底材料浸渍于热固性树脂中并使它干燥而制成的，而片状基底材料是由上述的电气绝缘非织造织物制成的。
通过加热加压形成预浸渍体层来形成本发明的层压板，该预浸渍体通过将薄片状基底材料浸渍在热固性树脂中并使它干燥而形成，该基底材料是通过上述电绝缘非织造织品组成。
具体实施本发明的最佳模式
下文将描述本发明的电气绝缘非织造织物的例子。
在这例子中，非织造织物是通过混合和对以下原料进行造纸生产来制成的：聚对苯二胺对苯酰胺纤维碎块，其纤维直径最好是1.5denier(旦)或更小；聚对苯二胺对苯酰胺纤维浆粕；以及由具有软化温度220℃或更高的热塑性树脂纤维碎块制成的第二粘合剂。然后，热固性树脂粘合剂被喷涂在造纸混合物非织造织物上以使各纤维互相粘结。通过使热固性树脂粘合剂粘附在各纤维的交叉点上而起到使纤维互相粘结的作用。作为第二粘合剂的热塑性树脂纤维碎块通过热熔化粘结使各纤维互相粘结或是通过由于各纤维热软化而变形使纤维缠结而实现的。由于热软化而生的这样的热熔化粘附和缠结可利用轧光工艺来实现，在轧光工艺中非织造织物纤维在热罗拉(轧辊)之间被施压。
希望聚对苯二胺对苯酰胺纤维碎块具有的纤维长度为3～6mm。当纤维长度变得较短时，纤维的粘结点减少，由此使非织造织物的弹性模数下降。另一方面，当纤维长度变得较长时，非织造织物的弹性模数就变得较高，但在造纸中发生纤维打结及分布不均匀，由此使非织造织物的密度变得不均匀。
热固性树脂粘合剂在非织造织物中的含量希望是5～30％(质量)。如果热固性树脂粘合剂的含量低于5％(质量)，则各纤维的粘结变弱。对热固性树脂粘合剂的5％(质量)含量的考虑是：当非织造织物被导入应用了热罗拉的轧光工艺中时，预先为非织造织物提供足够的强度，并且还考虑了保持无纺织的抗溶强度及防止在预浸渍体的制造工艺中膏状物成形不清。如热固性树脂粘合剂的含量超过30％(质量)，纤维容易在轧光工艺中粘附在热罗拉上并加强了预浸渍体的热收缩。因此，30％的热固性树脂粘合剂含量是考虑了易于管理在防止纤维粘附在热罗拉上情况下的非织造织物的密度以及在优选范围内控制预浸渍体的热收缩。尽管如此，并不禁止热固性树脂粘合剂的使用超过30％(质量)。
热固性树酯粘合剂可以是环氧树脂并具有作为固化剂的异氰酸酯树脂。在此情况下，环氧树脂与异氰酸树脂的掺和质量可以是这样，异氰酸酯树脂对环氧树脂之比为0.5～5∶10。环氧树脂粘合剂的固化反应平稳地逐渐进行，而仍未反应的官能团减少。这对减小因热导致预浸渍体的弹性模数的下降有利。
第二粘合剂在非织造织物中的含量，考虑到纤维互相间的有效粘结和防止预浸渍体的热收缩及层压板的翘曲及扭曲，最好是高些，但是考虑到层压板的抗热性而最好是较低些。第二粘合剂的含量最好是5～15％(质量)。
用作第二粘合剂并具有软化温度220℃或更高的热塑性树脂纤维碎块可以是：间芳族聚酰胺纤维(聚间苯二酰胺间苯二酰胺纤维)碎块，聚酯纤维碎块，尼龙6纤维，尼龙66纤维碎块，聚烯丙基醚纤维碎块或类似物，但它们不局限于此，只要它们是具有软化温度为220℃或更高的热塑性树脂纤维就可。该软化温度应是热分解温度或更低的温度。当间芳族聚酰胺纤维碎块被选作第二粘合剂时，其纤维直径希望是23denier(旦)或更小，同时其纤维长度希望是3～10mm。为使更多的地方的间芳族聚酰胺纤维热熔化和互相粘结或因它们的热软化而相互缠结，它们的纤维长度最好是长些；但当进行造纸操作时为使纤维的分布更佳，它们的纤维长度最好是短些。因此，考虑到这些纤维长度被加以适当的控制。
希望用作第二粘合剂的每一纤维碎块是“未展开的”。在本说明中，“未展开的”的意思包含：一是具有较小程度的未展开，以及另一个是在概念上是未展开的。利用未展开的纤维碎块，利用热罗拉更容易完成热熔粘结或缠结操作。
虽然第二粘合剂的形式可能是纤维浆粕或纤条体而不是上述的纤维碎块，但还是希望有纤维碎块，因为造纸法制的非织造织物具有更多的空隙并因此在生产层压板时使非织造织物有更佳的树脂浸渍。选择纤维碎块的视角是希望提高层压板的抗湿性及绝缘性。
通过应用上述的非织造织物作基底材料来制造层压板。首先，非织造织物用环氧树脂清漆浸渍并加热和干燥以生产预浸渍体。此后，一片预浸渍体或两片或更多片预浸渍体一个置于另一个上面地在加热及加压作用下成型。在此情况下，可把一种金属箔或多种金属箔置于预浸渍体的一个表面或多个表面上以形成金属箔包层层压板。
印刷电路板可通过蚀刻金属箔包层层压板以实施布线操作来制成。另外，多层印刷电路板是利用一种叠合系统通过应用多个预浸渍体层作为绝缘层来制造的。
本发明的一些例子将在下文中结合比较及现有技术一起进行描述。
(例子1)
(电气绝缘非织造织物的生产)
可在市场上从Du Pont公司买到商品名为KEVLAR的分布液下的及造纸法制的聚对二甲酰对苯二胺纤维碎块及浆粕，和从TEIJIN有限公司买到商品名为CONEX的聚间苯二甲酰间苯二胺纤维碎块。这些纤维具有的纤维直径为1.5denier(旦)，而纤维长度为3mm。聚对二甲酰对苯二胺纤维浆粕通过聚对二甲酰对苯二胺纤维碎块的打浆机而制成，以便具有50csf的打浆度。
本例子中应用的热固性树脂粘合剂包含的主要成份是：可在市场上从日本DAI-NIPPON INK AND CHEMICALS有限公司买到的商品名为“V COAT A”的环氧树脂乳剂，以及在市场上从同一公司买到的商品名“CR-60B”的块状异氰酸酯树脂。块状异氰酸酯树脂对环氧树脂的掺和质量(固化剂质量)比是1∶10。在以造纸法制造及加热和干燥之后，热固性树脂粘合剂被喷涂在上述纤维上以产出非织造织物。此后，当非织造织物通过一对加热罗拉组时在333℃温度及200KN/m线压力下被加热和压缩。
这个非织造织物的单位质量是72g/m2，聚对二甲酰对苯二胺纤维碎块对聚对二甲酰对苯二胺纤维浆粕的掺和质量比是80/20，热固性树脂粘合剂在非织造织物中的含量是17％(质量)，而第二粘合剂在非织造织物中的含量是9％(质量)[见表1(1)]
(预浸渍体的生产)
具有52％(质量)树脂含量的预浸渍体是通过以溴化双酚A型环氧树脂清漆浸渍上述非织造织物并对它们加热及干燥而制成的。
(层压板的生产)
把四层上述预浸渍体一个在另一个上面地叠合，并且把厚度18mm的上及下铜箔置于其上。它们在170℃温度及4MPa压力下成型以获得铜包层层压板。
(例子2～25及比较1)
除了聚对二甲酰对苯二胺纤维碎块/聚对二甲酰对苯二胺纤维浆粕的比例、聚对二甲酰对苯二胺纤维碎块的纤维长度、聚对二甲酰对苯二胺纤维浆粕的打浆度、热固性树脂粘合剂在非织造织物中的含量、第二粘合剂在非织造织物中含量以及热固性树脂粘合剂的固化剂质量是分别如表1(1)～1(6)的例子2～25所示而确定的之外，以与例子1相同的方式生产非织造织物，而预浸渍体及铜包层层压板以和例1相同的方式生产出来。
表1(1)
           例子      1      2     3      4      5
碎块/浆粕     80/20     0/100     45/55     50/50     90/10
纤维长度     3     3     3     3     3
打浆度(csf)     50     50     50     50     50
热固性树脂粘合剂(质量％)     17     17     17     17     17
第二粘合剂(质量％)     9     9     9     9     9
固化剂质量     1     1     1     1     1
表1(2)
          例子     6      7      8      9     10
碎块/浆粕     95/05     80/20     80/20     80/20     80/20
纤维长度     3     2     4     5     6
打浆度(csf)     50     50     50     50     50
热固性树脂粘合剂(质量％)     17     17     17     17     17
第二粘合剂(质量％)     9     9     9     9     9
固化剂质量     1     1     1     1     1
表1(3)
       例子     11     12     13      14     15
碎块/浆粕     80/20     80/20     80/20     80/20     80/20
纤维长度     7     3     3     3     3
打浆度(csf)     50     600     550     50     50
热固性树脂粘合剂(质量％)     17     17     17     17     17
第二粘合剂(质量％)     9     9     9     4     5
固化剂质量     1     1     1     1     1
表1(4)
           例子     16      17      18      19       20
碎块/浆粕     95/05     80/20     80/20     80/20     80/20
纤维长度     3     3     3     3     3
打浆度(csf)     50     50     50     50     50
热固性树脂粘合剂(质量％)     17     17     4     5     30
第二粘合剂(质量％)     15     16     9     9     9
固化剂质量     1     1     1     1     1
表1(5)
          例子      21      22      23      24     25
碎块/浆粕     80/20     80/20     80/20     80/20     80/20
纤维长度     3     3     3     3     3
打浆度(csf)     50     50     50     50     50
热固性树脂粘合剂(质量％)     40     17     17     17     17
第二粘合剂(质量％)     9     9     9     9     9
固化剂质量     1     6     5     0.5     0.4
表1(5)
   比较1
  碎块/浆粕     97/03
  纤维长度     3
  打浆度(csf)     50
  热固性树脂粘合剂(质量％)     17
  第二粘合剂(质量％)     9
  固化剂质量     1
(现有技术1)
除去应用于在市场上从日本TEIJIN有限公司买到商品名为TECHOLA的碎块作为聚对苯二甲酰-3，4’-二苯基醚对苯二酰胺纤维，在市场上从日本TEIJIN有限公司买到商品名为CONEX的碎块作为聚间苯二甲酰间苯二胺纤维，以及只使用与例子1中使用的相同热固性树脂粘合剂作为粘合剂之外，以和例子1相同的方式生产出非织造织物、预浸渍体及铜包层层压板。这种非织造织物的单位质量为72g/m2，并具有77％(质量)聚对苯二甲-3，4’-二苯基醚对苯二酰胺纤维碎块、15％(质量)聚间苯二甲酰间苯二胺纤维碎块及8％(质量)热固性树脂粘合剂的化合物成份。聚间苯二甲酰间苯二胺纤维碎块是热熔的并粘结在聚对苯二甲酰-3，4’-二苯基醚对苯二酰胺纤维碎块上。
(现有技术2)
除去应用了在市场上从日本TEIJIN有限公司买到商品名为KEVLAR作为聚对二甲酰对苯二胺纤维碎块，以及只使用与例子1中应用的相同热固性树脂粘合剂作为粘合剂之外，以和例子1相同的方式生产出非织造织物、预浸渍体及铜包层层压板。这种非织造织物的单位质量为72g/m2，并具有80％(质量)聚对二甲酰对苯二胺纤维碎块和20％(质量)热固性树脂粘合剂的化合物成份。热固性树脂粘合剂与聚对二甲酰对苯二胺纤维碎块互相粘结。
例子1～25、比较1和现有技术1及2的预浸渍体及铜包层层压板的特性的评价结果分别示于表2(1)～(6)。评价项目及评价方法如下。
(1)膏状物轮廓不清
在预浸渍体的两边覆盖PET薄膜，并从两边PET薄膜上加热以便叠合，并然后在以下条件下通过发射激光在浸渍体上制孔：脉冲宽度0.03ms，脉冲周期3ms，脉冲数3以及孔直径为0.2mm(制孔操作是在预浸渍体浮于空气中而不是置于支承座的状况下实施的)。这之后制成的孔被灌注铜膏，把PET薄膜从预浸渍体上除去。然后，预浸渍体在170℃温度和4MPa压力下制成之后，这样获得的孔壁的横截面可以被观察到。少量膏状物轮廓不清表明孔壁的粗糙度较小并因此该孔壁被精巧地加工成。
(2)尺寸变化率
在激光发射在预浸渍体上并在预浸渍体上以预定间隔制成两个标准孔之后，测量了两个孔之间的距离。然后，在预浸渍体的两面上覆盖PET薄膜而然后在其上加热以叠合预浸渍体。这之后测量孔之间的距离。在叠合之前及之后计算出孔之间距离的尺寸变化率。
(3)层压板的翘曲
具有厚度0.1mm及尺寸为330mm×500mm的铜包层层压板被施以蚀刻工艺而制备成印刷电路板，该印刷电路板在其前及后面分别具有比例为30％及80％的剩余铜面区域。在对这样制出的印刷电路板以120℃加热35分钟之后，然后把它们冷却，测量其翘曲。
(4)焊接抗热性
具有附着的铜箔和尺寸为25mm×25mm的试件被悬浮在300℃的焊接槽上。测出试件表面层产生空气泡然后表面隆起的时间。
(5)非织造织物的强度
在尺寸为250mm×15mm的非织造织物浸入丙酮5分钟之后，测量其拉伸强度。
(6)预浸渍体的弹性模数
测量尺寸为250mm×15mm的预浸渍体的拉伸弹性模数。
(7)纤维集束
非织造织物中纤维集束的消失用符号□标示，而非织造织物中纤维集束的出现用符号X标示。
表2(1)
          例子     1     2     3     4     5
膏状物轮廓不清(μm)     6     4     5     6     10
预浸渍体的尺寸变化率 长度宽度     -     -     -     -     -
    0.04     0.05     0.04     0.04     0.04
    1     -     3     5     5
    -     0.05     -     -     -
    0.04     -     0.04     0.04     0.04
    0     -     2     2     1
层压板的翘曲(mm)     5.7     5.0     5.3     5.5     5.6
焊接抗热性(min)     20     10     12     17     18
非织造织物强度(N/15mm)     60.0     64.3     61.2     60.3     48.3
预浸渍体的弹性模数(Gpa)     3.1     3.3     3.2     3.2     2.7
纤维集束     □     □     □     □     □
表2(2)
          例子     6     7     8     9     10
膏状物轮廓不清(μm)     16     5     6     6     7
预浸渍体的尺寸变化率 长度宽度     -     -     -     -     -
    0.05     0.04     0.04     0.04     0.04
    9     5     0     1     1
    -     -     -     -     -
    0.06     0.04     0.03     0.03     0.04
    1     2     9     9     0
层压板的翘曲(mm)     6.2     6.0     5.2     5.2     5.1
焊接抗热性(min)     18     20     20     20     20
非织造织物强度(N/15mm)     37.8     30.0     62.0     64.0     66.0
预浸渍体的弹性模数(Gpa)     2.4     1.5     3.3     3.6     3.8
纤维集束     □     □     □     □     □
表2(3)
         例子     11     12     13     14     15
膏状物轮廓不清(μm)     7     11     9     7     7
预浸渍体的尺寸变化率 长度宽度     -     -     -     -     -
    0.04     0.06     0.05     0.04     0.04
    3     0     4     4     6
    -     -     -     -     -
    0.04     0.05     0.05     0.04     0.04
    1     5     1     3     5
层压板的翘曲(mm)     5.0     6.0     5.8     14.0     8.0
焊接抗热性(min)     20     20     20     17     18
非织造织物强度(N/15mm)     68.0     39.4     45.0     58.0     56.9
预浸渍体的弹性模数(Gpa)     3.8     2.7     2.6     2.8     2.9
纤维集束     □     □     □     □     □
表2(4)
         例子     16     17     18     19     20
膏状物轮廓不清(μm)     6     6     15     10     5
预浸渍体的尺寸变化率 长度宽度     -     -     -     -     -
    0.04     0.04     0.04     0.04     0.04
    6     5     4     5     7
    -     -     -     -     -
    0.04     0.04     0.04     0.04     0.04
    4     4     2     2     3
层压板的翘曲(mm)     5.0     4.9     10.0     5.9     5.1
焊接抗热性(min)     16     10     19     20     20
非织造织物强度(N/15mm)     54.1     53.2     32.2     40.2     52.7
预浸渍体的弹性模数(Gpa)     2.9     2.9     2.4     2.7     3.1
纤维集束     □     □     □     □     □
表2(5)
         例子     21     22     23     24     25
膏状物轮廓不清(μm)     4     6     6     6     6
预浸渍体的尺寸变化率 长度宽度     -     -     -     -     -
    0.05     0.04     0.04     0.04     0.04
    2     3     5     5     6
    -     -     -     -     -
    0.05     0.04     0.04     0.04     0.04
    0     1     1     3     1
层压板的翘曲(mm)     5.4     8.0     5.5     5.5     5.6
焊接抗热性(min)     20     20     20     20     20
非织造织物强度(N/15mm)     70.8     49.9     56.3     40.0     25.0
预浸渍体的弹性模数(Gpa)     3.1     1.5     2.5     3.0     3.0
纤维集束     □     □     □     □     □
表2(5)
   比较1   现有技术1    现有技术2
膏状物轮廓不清(μm)     24     7     21
预浸渍体的尺寸变化率 长度宽度     -0.061     -0.085     -0.150
    -0.058     -0.066     -0.130
层压板的翘曲(mm)     16.0     32.0     24.0
焊接抗热性(min)     17     10     11
非织造织物强度(N/15mm)     22.0     24.5     24.5
预浸渍体的弹性模数(Gpa)     1.5     1.3     1.4
纤维集束     □     □     □
比较表1和表2，可以指出如下的制造条件和特别是完成本发明目的所需的条件：
应该特别指出：除了聚对二甲酰对苯二胺纤维碎块与聚对二甲酰对苯二胺纤维浆粕的掺和质量比之外，考虑到例子1～6及比较1的膏斑、层压板翘曲及非织造织物强度具有相同的制造条件，该聚对二甲酰对苯二胺纤维碎块与聚对二甲酰对苯二胺纤维浆粕的掺和质量比为0/100～95/5，但最好是50/50～90/10。还应指出，例子1及7～11具有相同的制造条件，聚对二甲酰对苯二胺纤维碎块的纤维长度除外，该碎块的纤维长度为2～7mm，但考虑到纤维斑点及预浸渍体的弹性模数，它最好是3至6mm。
相似地，应该指出，考虑到除聚对二甲酰对苯二胺纤维浆粕的打浆度外，例子1、12及13的非织造织物强度具有相同的制造条件，该聚对二甲酰对苯二胺纤维浆粕的打浆度为600csf或更小，但最好是550csf或更小。
除去第二粘合剂的质量百分之外，例子1及14～17具有相同的制造条件，在非织造织物中的第二粘合剂含量4～16％(质量)，但应指出考虑到层压板的翘曲以及在这些例子的比较中的焊接抗热性，它最好是5～15％(质量)。
除去热固性树脂粘合剂的含量之外，例子1及18～21具有相同的制造条件，在非织造织物中的热固性树脂粘合剂的含量是4～40％(质量)，但应该指出考虑到这些例子的比较中的非织造织物强度及预浸渍体的尺寸变化率，它最好是5～30％(质量)。
在例子1及22～25中，在热固性树脂粘合剂是具有异氰酸酯树脂固化剂的环氧树脂的情况下，环氧树脂与异氰酸酯树脂的掺和质量是：异氰酸酯树脂0.4～6对环氧树脂10，但应该指出，从这些例子的比较中的非织造织物强度及预浸渍体的弹性模数角度看，它最好是：异氰酸酯树脂0.5～5对环氧树脂10。
如上所述，当预浸渍体上及具有电气绝缘非织造织物作基底材料的绝缘层上的制孔操作是利用发射激光来进行时，该孔壁可以更好的方式来完成。还可以防止因热产生的预浸渍体尺寸变化和因热产生的层压板翘曲以减小变化和翘曲。
工业的应用可能性
本发明的非织造织物适用于其上表面安装有各种电子装置的印刷电路板，并且特别适用于多层印刷电路板的预浸渍体及层压板。

Claims (10)

1.一种电气绝缘非织造织物具有对芳族聚酰胺纤维主要成份，该对芳族聚酰胺纤维以热固性树脂粘合剂及第二粘合剂互相粘结，该第二粘合剂是从具有软化温度220℃或更高的热塑性树脂的纤维碎块、纤维浆粕及纤条体中选出的一种粘合剂，所述对芳族聚酰胺纤维的特点是包含聚对苯二胺对苯酰胺纤维浆粕或聚对苯二胺对苯酰胺纤维碎块及聚对苯二胺对苯酰胺纤维浆粕两者，该两者的掺和质量比是：所述聚对苯二胺对苯酰胺纤维碎块对所述聚对苯二胺对苯酰胺纤维浆粕为0/100～95/5。
2.如权利要求1所述的电气绝缘非织造织物，其特征在于：所述聚对苯二胺对苯酰胺纤维浆粕的打浆度是550csf或更小。
3.如权利要求2所述的电气绝缘非织造织物，其特征在于：所述聚对苯二胺对苯酰胺纤维碎块对所述聚对苯二胺对苯酰胺纤维浆粕的掺和质量比是50/50～90/10。
4.如权利要求3所述的电气绝缘非织造织物，其特征在于：所述聚对苯二胺对苯酰胺纤维碎块的纤维长度是3～6mm。
5.如权利要求1所述的电气绝缘非织造织物，其特征在于：在所述非织造织物中的所述热固性树脂粘合剂的含量是5～30％(质量)。
6.如权利要求5所述的电气绝缘非织造织物，其特征在于：所述热固性树脂粘合剂是环氧树脂并且含有异氰酸酯树脂作固化剂，所述环氧树脂与所述异氰酸酯树脂的掺和质量为：0.5～5所述异氰酸酯树脂对10所述环氧树脂。
7.如权利要求5所述的电气绝缘非织造织物，其特征在于：在所述非织造织物中的所述第二粘合剂的含量是5～15％(质量)。
8.如权利要求6所述的电气绝缘非织造织物，其特征在于：在所述非织造织物中的所述第二粘合剂的含量是5～15％(质量)。
9.一种预浸渍体，包括用热固性树脂浸渍并使之干燥的片状基底材料，而所述片状基底材料的特点是：它是如权利要求1～8中任一条所述的电气绝缘非织造织物。
10.一种层压板包括一层或多层在加热及加压下制成的预浸渍体，所述预浸渍体被制成以热固性树脂浸渍并使之干燥的片状材料，而所述片状基底材料是如权利要求1～8任一条所述的电气绝缘非织造织物。
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