JP2005213656A - Glass cloth - Google Patents
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- JP2005213656A JP2005213656A JP2004018444A JP2004018444A JP2005213656A JP 2005213656 A JP2005213656 A JP 2005213656A JP 2004018444 A JP2004018444 A JP 2004018444A JP 2004018444 A JP2004018444 A JP 2004018444A JP 2005213656 A JP2005213656 A JP 2005213656A
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- 239000011521 glass Substances 0.000 title claims abstract description 137
- 239000004744 fabric Substances 0.000 title claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 22
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
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- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 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
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
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- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 239000005337 ground glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 239000011256 inorganic filler Substances 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
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- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- -1 prepreg Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Woven Fabrics (AREA)
Abstract
Description
本発明は電子・電気分野で使用されるプリント配線板に用いられるガラスクロスに関する。 The present invention relates to a glass cloth used for a printed wiring board used in the electronic / electric field.
プリント配線板の分野においては、電子機器の小型化に伴ない、単層のフィルム状基板、及び多層配線板を製造するために使用されるプリプレグの薄型化要求が、近い将来、最小厚さで１５μｍ以上２０μｍ以下に達するものと予測されている。このプリプレグにおいては、その薄さと、機械的特性、特に高剛性、及び高寸法安定性、並びに低熱膨張率とを両立させるために、ガラスクロスの使用が必須になるものと思われるが、上記の最小厚さを満たすためには、該ガラスクロスの厚さを１５μｍ未満にする必要がある。
ところで、極薄地ガラスクロスとしては、厚さが２５μｍ以下（好ましい厚さは１５〜２０μｍ）で、且つ、タテ糸またはヨコ糸の少なくともどちらか一方が、隣り合う糸同士が実質的に隙間無く配列されているガラスクロスが提案されている（特許文献１参照）。
上記特許文献１の実施例に記載されたガラスクロスは、平均フィラメント径３．５〜４．５μｍ、構成フィラメント数１００本のガラス糸を７５〜１００本／２５ｍｍの織密度で製織し、高圧散水流によって開繊加工することにより得られたものであり、厚さが１７〜２１μｍであったことが開示されている。
In the field of printed wiring boards, with the miniaturization of electronic equipment, the demand for thin prepregs used for manufacturing single-layer film-like substrates and multilayer wiring boards is expected to become the smallest in the near future. It is predicted to reach 15 μm or more and 20 μm or less. In this prepreg, it seems that the use of glass cloth is indispensable in order to achieve both the thinness and mechanical properties, particularly high rigidity and high dimensional stability, and low thermal expansion coefficient. In order to satisfy the minimum thickness, the thickness of the glass cloth needs to be less than 15 μm.
By the way, as an ultra-thin ground glass cloth, the thickness is 25 μm or less (preferably the thickness is 15 to 20 μm), and at least one of the warp yarn and the weft yarn is arranged so that adjacent yarns are arranged substantially without gaps. A glass cloth has been proposed (see Patent Document 1).
The glass cloth described in the examples of the above-mentioned Patent Document 1 is made by weaving glass yarn having an average filament diameter of 3.5 to 4.5 μm and a number of constituting filaments of 100 at a weaving density of 75 to 100 pieces / 25 mm, It is obtained by opening the fiber with a water flow, and it is disclosed that the thickness was 17 to 21 μm.
また、単位面積当たりの質量が１６×１０-3〜８０×１０-3（Ｋｇ／ｍ2 ）であって、ガラスクロスが占有する空間においてマトリックス樹脂が含浸可能な空隙の割合が４７〜６１％であり、たて糸の開繊率が６０％以上１００％未満、且つよこ糸の開繊率が９０％以上１００％以下であるガラスクロスが提案されている（特許文献２参照）。該特許文献２には、「２３×１０-3では、厚さ２１（μｍ）程度（段落番号００３３）」との記載があるので、仮に厚さが質量に比例するものとすると、上記質量の下限１６×１０-3Ｋｇ／ｍ2 は厚さ１５μｍ程度に相当することになる。
上記特許文献２の実施例（表８）に記載されたガラスクロスは、平均フィラメント径４μｍ、構成フィラメント数１００本のガラス糸を６９〜７２本／２５ｍｍの織密度で製織し、ローラー及びテンションフリー開繊加工の組合せ、又は超音波開繊加工によって得られたものであり、厚さが２１〜２２μｍであったことが開示されている。
すなわち、上記特許文献１、又は特許文献２記載の先行技術においては、厚み１５μｍ未満のガラスクロス、及びその製造方法は具体的には開示されていない。
Further, the mass per unit area is 16 × 10 −3 to 80 × 10 −3 (Kg / m 2 ), and the ratio of voids that can be impregnated with the matrix resin in the space occupied by the glass cloth is 47 to 61%. A glass cloth having a warp yarn opening rate of 60% to less than 100% and a weft yarn opening rate of 90% to 100% has been proposed (see Patent Document 2). In Patent Document 2, there is a description that “23 × 10 −3 has a thickness of about 21 (μm) (paragraph number 0033)”. Therefore, if the thickness is proportional to the mass, The lower limit of 16 × 10 −3 Kg / m 2 corresponds to a thickness of about 15 μm.
The glass cloth described in the example (Table 8) of the above-mentioned patent document 2 is made by weaving glass yarns having an average filament diameter of 4 μm and 100 constituent filaments at a weaving density of 69 to 72/25 mm. It is disclosed that it was obtained by a combination of fiber opening processing or ultrasonic fiber opening processing and had a thickness of 21 to 22 μm.
That is, in the prior art described in Patent Document 1 or Patent Document 2, a glass cloth having a thickness of less than 15 μm and a manufacturing method thereof are not specifically disclosed.
本発明の目的は厚さが１５μｍ未満のプリント配線板用ガラスクロス、及び該ガラスクロスを用いたプリプレグ、あるいは該プリプレグを硬化させてなる、寸法安定性、機械的特性に優れたフィルム状基板を提供することにある。 An object of the present invention is to provide a glass cloth for a printed wiring board having a thickness of less than 15 μm, a prepreg using the glass cloth, or a film-like substrate excellent in dimensional stability and mechanical properties obtained by curing the prepreg. It is to provide.
前述した特許文献１、または特許文献２においては、マトリックス樹脂の含浸量を減少させ機械特性の向上や熱伝導率の低下をはかる、絶縁信頼性を確保する、あるいはレーザー加工性のばらつきを減少させる等の目的で、構成フィラメント数の多い糸を開繊加工によって拡幅することによって、バスケットホール（タテ糸もヨコ糸も分布しない部分）の面積割合の少ないガラスクロスを得ることが主眼となっている。
本発明者らが検討した結果、上記手法によっては厚さが１５μｍ未満、かつ寸法安定性、機械的特性に優れたフィルム状基板を得ることができるガラスクロスを作成することが困難であることを見出した。即ち、上記手法によって厚さが１５μｍ未満のガラスクロスを得るためには、織密度を下げた上でより強い条件の開繊加工を行って糸幅を拡幅し厚み方向のフィラメント数を減少させる必要があるが、このような拘束力が弱い状態に製織されたガラスクロスを強い条件で開繊加工した場合には目曲がりが発生しやすく、該ガラスクロスを用いたプリプレグからは寸法安定性に優れたフィルム状基板を得ることができなかった。
In Patent Document 1 or Patent Document 2 described above, the impregnation amount of the matrix resin is decreased to improve the mechanical characteristics and the thermal conductivity, to ensure insulation reliability, or to reduce the variation in laser processability. For the purpose of, etc., the main purpose is to obtain a glass cloth with a small area ratio of the basket hole (portion where neither warp yarn nor weft yarn is distributed) by widening a yarn having a large number of constituent filaments by opening processing. .
As a result of investigations by the present inventors, it is difficult to produce a glass cloth that can obtain a film-like substrate having a thickness of less than 15 μm and excellent dimensional stability and mechanical properties depending on the above method. I found it. That is, in order to obtain a glass cloth having a thickness of less than 15 μm by the above method, it is necessary to reduce the number of filaments in the thickness direction by expanding the yarn width by performing fiber opening under stronger conditions after lowering the weave density. However, when a glass cloth woven in such a low binding force is opened under strong conditions, bending tends to occur, and prepreg using the glass cloth has excellent dimensional stability. A film-like substrate could not be obtained.
そこで、目曲がりが発生しないような穏やかな条件で開繊加工することで糸幅を拡幅し厚み方向のフィラメント数を減少させるべく検討を重ねた結果、糸の撚りの部分で拡幅率が低下すること、及びガラスクロスを構成するガラス糸のフィラメント数の違いにより拡幅率が異なることを見出した。この知見に基づき、構成フィラメント数の少ない糸を穏やかな条件の開繊加工によって拡幅してある程度のバスケットホールを許容するガラスクロスとすることで厚さ１５μｍ未満を達成すると共に、このガラスクロスを用いたプリプレグを硬化させてなるフィルム状基板において優れた機械特性を保持することを見出し、本発明を完成するに至った。
即ち、本発明は以下のものである。
１．タテ糸及びヨコ糸の両方の平均フィラメント径が２．５μｍ以上であり、その少なくとも片方の平均フィラメント径が４．５μｍ未満であり、且つタテ糸及びヨコ糸の両方のフィラメント数が５本以上７０本以下のガラスヤーンで構成されるガラスクロスであって、厚さが５μｍ以上１５μｍ未満で、且つ表面ガラス糸被覆率が５０％以上１００％以下であることを特徴とするガラスクロスを提供する。
２．上記１に記載のガラスクロスとマトリックス樹脂からなるプリプレグを提供する。
３．上記２に記載のプリプレグを硬化してなるフィルム状基板を提供する。
Therefore, as a result of repeated investigations to widen the yarn width and reduce the number of filaments in the thickness direction by opening the fiber under mild conditions that do not cause bending, the widening rate decreases at the twisted portion of the yarn. It has been found that the widening ratio varies depending on the difference in the number of filaments of the glass yarn constituting the glass cloth. Based on this knowledge, we achieved a thickness of less than 15 μm by widening a yarn with a small number of constituent filaments by a gentle opening process to allow a certain amount of basket holes. The present inventors have found that excellent mechanical properties are maintained in a film-like substrate obtained by curing a prepreg that has been used, and have completed the present invention.
That is, the present invention is as follows.
1. The average filament diameter of both the warp yarn and the weft yarn is 2.5 μm or more, the average filament diameter of at least one of them is less than 4.5 μm, and the number of both the warp yarn and the weft yarn is 5 or more and 70 A glass cloth composed of the following glass yarns having a thickness of 5 μm or more and less than 15 μm and a surface glass yarn coverage of 50% or more and 100% or less is provided.
2. A prepreg comprising the glass cloth and the matrix resin as described in 1 above is provided.
3. A film-like substrate obtained by curing the prepreg described in 2 above is provided.
本発明のガラスクロスは厚さが１５μｍ未満で且つ目曲がり量が小さいため、該ガラスクロスを用いたプリプレグを硬化させることで寸法安定性、機械的特性に優れたフィルム状基板を提供することができる。 Since the glass cloth of the present invention has a thickness of less than 15 μm and a small amount of bending, it is possible to provide a film-like substrate having excellent dimensional stability and mechanical properties by curing a prepreg using the glass cloth. it can.
以下本発明について具体的に説明する。
ガラスクロスの厚さは、該ガラスクロスを構成するタテ糸とヨコ糸との交点における厚さ方向（以下、「Ｚ方向」ともいう。）に配列される平均フィラメント本数により決まる。即ち、例えば厚さ２０μｍを達成するためには、フィラメント径が４．０μｍの原糸で構成されれば、交点においてＺ方向に配列される平均フィラメント本数をタテ糸とヨコ糸あわせて５本にすることにより、２０μｍの厚さを得ることができる。本発明においては、厚さが２０μｍ以下のプリプレグを製造するにあたって、ガラスクロスの表層に樹脂のみからなる層を２．５μｍ超に保持させることが好ましいため、ガラスクロスの厚さは５μｍ以上１５μｍ未満が好ましく、７μｍ以上１２μｍ以下の厚さがより好ましい。
The present invention will be specifically described below.
The thickness of the glass cloth is determined by the average number of filaments arranged in the thickness direction (hereinafter also referred to as “Z direction”) at the intersection of the warp yarn and the weft yarn constituting the glass cloth. That is, for example, in order to achieve a thickness of 20 μm, if the filament diameter is composed of 4.0 μm, the average number of filaments arranged in the Z direction at the intersection is 5 including the warp and the weft. By doing so, a thickness of 20 μm can be obtained. In the present invention, when manufacturing a prepreg having a thickness of 20 μm or less, it is preferable to hold a layer made only of resin on the surface layer of the glass cloth at a thickness of more than 2.5 μm, and thus the thickness of the glass cloth is 5 μm or more and less than 15 μm. A thickness of 7 μm or more and 12 μm or less is more preferable.
このことから交点におけるＺ方向の平均フィラメント数は、平均フィラメント径３．５μｍのフィラメントを用いた場合でも約４本以下にまで減らさなければならず、大きな加工力を有する扁平化加工が必要となるものであった。しかしながら、本発明のガラスクロスは極めて薄いガラスクロスであり、タテ糸とヨコ糸の拘束力が低いため、大きな加工力を加えた場合には目曲がりが発生しやすい。 そのために、本発明のガラスクロスにおいては、ガラス糸を構成するフィラメント数を低減することで、小さい加工力でも拡幅できるようにした。
即ち、ガラスクロスの製織に使用するガラス糸は、通常は糸強度保持のため１ｉｎｃｈに１回撚りを加えている。しかしながら、開繊加工等の扁平化加工を行った場合に、この撚りの部分で局所的に拡幅率が下がり、Ｚ方向のフィラメント本数を減らすことができなくなる。本発明者らは鋭意検討した結果、構成するガラス糸のフィラメント数の違いにより拡幅率が異なることを見出した。即ち、フィラメント数が多いガラス糸を用いた場合、撚りの部分はフィラメントの拘束力が高くなる部分が多くなっており、拡幅率の低下を招く。それに対して、フィラメント数の少ないガラス糸を用いた場合、フィラメント数が少ない分、同じ撚り数であっても撚りが及ぼすフィラメントの拘束力が減少することで拡幅率が上がり、Ｚ方向のフィラメント本数を減少させることができたと考察される。
For this reason, the average number of filaments in the Z direction at the intersection must be reduced to about 4 or less even when filaments having an average filament diameter of 3.5 μm are used, and flattening with a large processing force is required. It was a thing. However, the glass cloth of the present invention is an extremely thin glass cloth and has a low binding force between the warp yarn and the weft yarn. Therefore, when a large processing force is applied, the glass cloth is likely to be bent. Therefore, in the glass cloth of the present invention, the number of filaments constituting the glass yarn is reduced so that the width can be increased even with a small processing force.
That is, the glass yarn used for weaving the glass cloth is usually twisted once per inch to maintain the yarn strength. However, when a flattening process such as a fiber opening process is performed, the widening rate is locally reduced at the twisted portion, and the number of filaments in the Z direction cannot be reduced. As a result of intensive studies, the present inventors have found that the widening ratio differs depending on the difference in the number of filaments of the glass yarn to be formed. That is, when a glass yarn having a large number of filaments is used, the twisted portion has a larger portion where the binding force of the filament is increased, resulting in a decrease in the widening ratio. On the other hand, when glass filaments with a small number of filaments are used, the width of the filament increases in the Z direction because the binding force exerted by the twist decreases even if the number of twists is the same, and the number of filaments in the Z direction increases. Is considered to have been reduced.
上記考察をふまえて後述する偏平加工条件下で実験を行った結果、本発明のガラスクロスの厚さを得るためにはＺ方向の平均フィラメント本数を約４本以下にする必要があることから、これを満たすことができるタテ糸及びヨコ糸のフィラメント本数は５本以上７０本以下が好ましく、３０本以上６０本以下がより好ましく、４０本以上５０本以下が最も好ましい。
フィラメント本数が５本未満の場合、該フィラメントで構成されるガラス糸の強度の保持が難しく、７０本よりフィラメント数を多くすれば、ガラスクロスの厚みを１５μｍ未満にすることが難しくなる。
また、ガラスクロスの厚みを薄くするためには、ガラスクロスを構成する糸（ヤーン）の平均フィラメント径が細い方が効果的である。具体的には、タテ糸及びヨコ糸のいずれか一方、もしくは両方の平均フィラメント径が４．５μｍ未満が好ましく、４．１μｍ以下がより好ましい。また、タテ糸及びヨコ糸の両方の平均フィラメント径が４．５μｍ未満がより好ましく、４．１μｍ以下がさらに好ましい。
As a result of conducting an experiment under the flat processing conditions described below based on the above consideration, in order to obtain the thickness of the glass cloth of the present invention, it is necessary to reduce the average number of filaments in the Z direction to about 4 or less. The number of warp and weft filaments that can satisfy this is preferably 5 or more and 70 or less, more preferably 30 or more and 60 or less, and most preferably 40 or more and 50 or less.
When the number of filaments is less than 5, it is difficult to maintain the strength of the glass yarn composed of the filaments. When the number of filaments is increased from 70, it is difficult to make the thickness of the glass cloth less than 15 μm.
In order to reduce the thickness of the glass cloth, it is effective that the average filament diameter of the yarn (yarn) constituting the glass cloth is narrow. Specifically, the average filament diameter of either one or both of the warp yarn and the weft yarn is preferably less than 4.5 μm, and more preferably 4.1 μm or less. Further, the average filament diameter of both the warp yarn and the weft yarn is more preferably less than 4.5 μm, further preferably 4.1 μm or less.
また、タテ糸、及びヨコ糸の平均フィラメント径の下限は、２．５μｍ以上が好ましく、３．５μｍ以上がより好ましい。タテ糸、又はヨコ糸のいずれかの糸の平均フィラメント径が２．５μｍ未満の場合は該糸のフィラメント強度が低いため毛羽が発生しやすく、タテ糸、及びヨコ糸のいずれか一方、もしくは双方の平均フィラメント径が４．５μｍより大きい場合は厚さ１５μｍ未満を達成することが困難になる。
また、ガラスクロスとして用いられるためには、目曲がりのないガラスクロス構造が重要である。ここで、目曲がり量とは、ガラスクロスの幅方向に平行に定規を配置して、等間隔にタテ糸が並んだと仮定した場合の糸の位置と、実際のタテ糸の位置とのずれの最大量をいう。そのためには、以下に定義する表面ガラス被覆率が５０％〜１００％であることが好ましく、７０％〜１００％であることがより好ましい。
Further, the lower limit of the average filament diameter of the warp yarn and the weft yarn is preferably 2.5 μm or more, and more preferably 3.5 μm or more. If the average filament diameter of either the warp yarn or the weft yarn is less than 2.5 μm, fluff is likely to occur because the filament strength of the yarn is low, and either one or both of the warp yarn and the weft yarn When the average filament diameter is greater than 4.5 μm, it is difficult to achieve a thickness of less than 15 μm.
Further, in order to be used as a glass cloth, a glass cloth structure without bending is important. Here, the amount of bending is the deviation between the actual warp yarn position and the actual warp yarn position when it is assumed that a ruler is arranged in parallel to the width direction of the glass cloth and the warp yarns are arranged at equal intervals. The maximum amount of. For that purpose, the surface glass coverage defined below is preferably 50% to 100%, more preferably 70% to 100%.
ここで言う表面ガラス被覆率（％）とは表面より観察した際のタテ糸またはヨコ糸の少なくともいずれかで被覆されている面積の比率を表したもので、具体的には表面観察により測定されたタテ糸幅（ＴＷ）、ヨコ糸幅（ＹＷ）、タテ糸−タテ糸隙間量（ＴＳ）、ヨコ糸−ヨコ糸隙間量（ＹＳ）より、（ＴＷ・ＹＷ＋ＹＷ・ＴＳ＋ＴＷ・ＹＳ）×１００／（（ＴＷ＋ＴＳ）・（ＹＷ＋ＴＳ））で算出される。
このようなガラスクロスを使用することで、厚さ約２０μｍ以下のプリプレグが得られ、それを硬化させることでフィルム状基板が得られる。また、前述したように表面ガラス被覆率を高くすることで、目曲がり等の欠点が減少し、樹脂固着ムラが改善され、寸法安定性に極めて良好な基板を得ることができる。
The surface glass coverage (%) here refers to the ratio of the area covered with at least one of warp and weft when observed from the surface. Specifically, it is measured by surface observation. Warp Thread Width (TW), Weft Thread Width (YW), Warp Yarn-Warp Yarn Clearance (TS), Weft Yarn-Weft Yarn Clearance (YS), (TW · YW + YW · TS + TW · YS) × 100 / It is calculated by ((TW + TS) · (YW + TS)).
By using such a glass cloth, a prepreg having a thickness of about 20 μm or less is obtained, and a film-like substrate is obtained by curing the prepreg. In addition, as described above, by increasing the surface glass coverage, defects such as bending are reduced, unevenness of resin adhesion is improved, and a substrate with extremely good dimensional stability can be obtained.
本発明のガラスクロスを得るためには、１．０回／インチの撚り数を有するガラス糸でも可能ではあるが、ガラス糸の撚り数を好ましくは０〜０．７回／インチ、より好ましくは０〜０．５回／インチ、さらに好ましくは０〜０．３回／インチに低撚糸化することが望ましい。低撚糸化により、より糸幅は拡がり易く、ガラスクロスの厚みが低減しやすくなる。また、低撚糸を使用することにより、糸が扁平化し、糸自体の断面形状が楕円の形状から平板の形状に近づき、ガラスクロス中のガラス繊維の分布がより均一となる。
また、本発明のガラスクロスを製造するにあたっては、製織したガラスクロスに、水流の圧力による開繊、液体を媒体とした高周波の振動による開繊、連続超音波加工開繊、ロールによる加圧での加工等の扁平化加工を施すことが好ましい。水流の圧力による開繊を使用する場合は、加工圧は０．５〜３．０ＭＰａが好ましい。加工圧が０．５ＭＰａ以下であると開繊の効果が充分でなく薄いガラスクロスをえることが困難になる。また３．０ＭＰａ以上の場合は目曲がりが発生する恐れがある。
In order to obtain the glass cloth of the present invention, a glass yarn having a twist number of 1.0 times / inch is possible, but the twist number of the glass yarn is preferably 0 to 0.7 times / inch, more preferably It is desirable to reduce the twist to 0 to 0.5 times / inch, more preferably 0 to 0.3 times / inch. By reducing the twisted yarn, the yarn width is more easily expanded and the thickness of the glass cloth is easily reduced. Further, by using a low twist yarn, the yarn is flattened, the cross-sectional shape of the yarn itself approaches the shape of a flat plate from an elliptical shape, and the distribution of the glass fibers in the glass cloth becomes more uniform.
In manufacturing the glass cloth of the present invention, the woven glass cloth is opened by water flow pressure, opened by high-frequency vibration using a liquid medium, opened by continuous ultrasonic processing, and pressed by a roll. It is preferable to apply a flattening process such as the above process. When using the opening by the pressure of a water flow, the processing pressure is preferably 0.5 to 3.0 MPa. If the processing pressure is 0.5 MPa or less, the opening effect is not sufficient and it becomes difficult to obtain a thin glass cloth. Further, when the pressure is 3.0 MPa or more, there is a risk of bending.
該扁平化加工により、より糸幅は拡がり、ガラス被覆率を高くしやすくなる。 また、糸が扁平化してＺ方向のフィラメント分布が減るので１５μｍ未満という厚みを達成しやすくなると共に、糸自体の断面形状が楕円の形状から平板の形状に近づき、ガラスクロス中のガラス繊維の分布がより均一となるという、糸の低撚糸化と同様の効果が得られる。
なお、上記の扁平化加工を行う場合には、搬送のためにガラスクロスにかかる張力が０．１〜３０Ｎ／ｍであることが好ましく、１〜１０Ｎ／ｍであることがより好ましい。そのためには、通常使用されるロール型の搬送装置のかわりに、たとえば特表平１１−５０７９９５号公報に記載されたコンベア型の搬送装置を使用することができる。
By the flattening process, the yarn width is further expanded and the glass coverage is easily increased. Also, since the yarn is flattened and the filament distribution in the Z direction is reduced, it is easy to achieve a thickness of less than 15 μm, and the cross-sectional shape of the yarn itself approaches the shape of a flat plate from an elliptical shape, and the distribution of glass fibers in the glass cloth The same effect as that of lower twisting yarn can be obtained.
In addition, when performing said flattening process, it is preferable that the tension concerning a glass cloth for conveyance is 0.1-30 N / m, and it is more preferable that it is 1-10 N / m. For this purpose, for example, a conveyor type conveying device described in JP-T-11-507995 can be used in place of the normally used roll type conveying device.
さらに、ガラス糸に滑剤の特性を示す有機物が付着した状態のガラスクロス、または通常のガラスクロスを製織する際に使用されるバインダー、糊剤等が付着した状態（通常、生機という）での扁平化加工やこれらの手法の組み合わせによって、より効果的となる。また、両手法の組み合わせにより、さらに効果的となる。
ここで、製織されるガラス原糸に付着している１次サイジング剤は、でんぷん系サイジング剤あるいは水溶性エポキシサイジング剤、もしくはこれらの成分の１次サイジング剤としての効果を阻害しない、潤滑成分、帯電防止剤等の成分を好適に添加したものが好ましい。また、１次サイジング剤のガラス繊維に対する付着量としては、０．０５質量％以上１０．０質量％以下、好ましくは糸強度、取り扱い性を考慮すれば０．１０質量％以上７．０質量％以下、さらに０．１５質量％以上５．０質量％以下が特に好ましい。
In addition, a glass cloth in which organic substances exhibiting the properties of a lubricant are adhered to glass yarn, or a flat state in which a binder, glue, etc. used when weaving ordinary glass cloth are adhered (usually called raw machinery). It becomes more effective by the combination processing and combination of these methods. Moreover, it becomes more effective by the combination of both methods.
Here, the primary sizing agent adhering to the glass yarn to be woven is a starch-based sizing agent or a water-soluble epoxy sizing agent, or a lubricating component that does not hinder the effects of these components as a primary sizing agent, What added suitably components, such as an antistatic agent, is preferable. The amount of the primary sizing agent attached to the glass fiber is 0.05% by mass or more and 10.0% by mass or less, preferably 0.10% by mass or more and 7.0% by mass in consideration of yarn strength and handleability. Hereinafter, 0.15% by mass or more and 5.0% by mass or less is particularly preferable.
さらに、ガラスクロスの通常実施される表面処理としてガラスクロスの風合いを固くする処理、例えば表面処理剤の付着量を上げる、被膜性の高い表面処理剤を使用する、表面処理剤に一般に使用されるシランカップリング剤のシラノール基の縮重合度合いを上げる等、もしくはガラス糸の目止め効果を有する処理等を実施することでガラスクロスの取り扱い性は向上させることができる。
本発明のプリプレグを製造するには、定法に従えばよい。例えば、ガラスクロスにエポキシ樹脂のようなマトリックス樹脂を有機溶剤で希釈した熱硬化性樹脂ワニス（以下、単に「ワニス」ともいう。）を含浸した後、乾燥炉にて有機溶剤を揮発させ、熱硬化性樹脂をＢステージ（半硬化状態）まで硬化させたプリプレグを作ればよい。この際に極力ガラスクロスに張力を与えないようにすると、さらに寸法安定性に優れたプリプレグを得ることができるのでより好ましい。なお、ガラスクロスへのマトリックス樹脂付着量は、ワニスの固形分とガラスクロスの質量の合計に対して、ワニス固形分の質量が２０質量％から８０質量％になるようにするのが好ましい。
Further, as a commonly performed surface treatment of glass cloth, it is generally used for a treatment for hardening the texture of the glass cloth, for example, using a surface treatment agent having a high coating property, increasing the adhesion amount of the surface treatment agent. The handling property of the glass cloth can be improved by increasing the degree of polycondensation of the silanol groups of the silane coupling agent or by performing a treatment having a sealing effect on the glass yarn.
In order to produce the prepreg of the present invention, a conventional method may be followed. For example, after impregnating a glass cloth with a thermosetting resin varnish (hereinafter also simply referred to as “varnish”) obtained by diluting a matrix resin such as an epoxy resin with an organic solvent, the organic solvent is volatilized in a drying furnace, What is necessary is just to make the prepreg which hardened curable resin to B stage (semi-hardened state). At this time, it is more preferable to prevent tension from being applied to the glass cloth as much as possible, because a prepreg having further excellent dimensional stability can be obtained. The amount of the matrix resin attached to the glass cloth is preferably such that the mass of the varnish solid content is 20% by mass to 80% by mass with respect to the total mass of the varnish solid content and the glass cloth mass.
本発明のフィルム状基板を製造するには、上記プリプレグを圧縮成型により硬化させる等の定法に従えばよい。この時に回路パターンを形成するための銅箔等を片側、もしくは両側に積層してもよい。また、上記プリプレグを複数枚積層して多層プリント回路板を作成することも可能である。
本発明のプリプレグ、あるいはフィルム状基板に使用されるマトリックス樹脂としては、エポキシ樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、ＢＴ樹脂、シアネート樹脂等の熱硬化性樹脂や、ＰＰＯ樹脂、ポリエーテルイミド樹脂、フッ素樹脂等の熱可塑性樹脂、またはそれらの混合樹脂などが挙げられる。また、樹脂中に水酸化アルミニウム、タルク等の無機充填剤を混在させた樹脂を使用しても構わない。しかしながら、本発明の目的から、マトリックス樹脂は可撓性に優れた樹脂が好ましい。
In order to produce the film-like substrate of the present invention, a conventional method such as curing the prepreg by compression molding may be followed. At this time, a copper foil or the like for forming a circuit pattern may be laminated on one side or both sides. It is also possible to produce a multilayer printed circuit board by laminating a plurality of the prepregs.
As the matrix resin used for the prepreg or film-like substrate of the present invention, thermosetting resins such as epoxy resin, unsaturated polyester resin, polyimide resin, BT resin, cyanate resin, PPO resin, polyetherimide resin, A thermoplastic resin such as a fluororesin, or a mixed resin thereof may be used. Moreover, you may use resin which mixed inorganic fillers, such as aluminum hydroxide and a talc, in resin. However, for the purpose of the present invention, the matrix resin is preferably a resin having excellent flexibility.
以下、本発明を実施例により詳しく説明する。
実施例、比較例中のガラスクロスの物性、ガラスクロスを用いたフィルム状基板の作成方法、及び試験方法は以下の方法により測定した。
１．ガラスクロスの物性測定方法：
ＪＩＳ Ｒ３４２０に従い測定した。
２．ガラスクロスの目曲がり量測定方法：
１００ｍ長のガラスクロスにおいて、１０ｍごとに１０箇所の目曲がり量を測定し、その平均目曲がり量を求めた。
３．プリプレグの作成方法：
ガラスクロスに、下記調合割合で調整したエポキシ樹脂ワニスを浸漬し、各ガラスクロス厚さの２倍のスリットで余剰樹脂ワニスを掻き落とし、１７０℃で３分間乾燥させてプリプレグを得た。
［エポキシ樹脂ワニス調合割合] ５０４６Ｂ８０（ジャパンエポキシレジン株式会社製、商品名）：７０質量％、１８０Ｓ７５Ｂ７０（ジャパンエポキシレジン株式会社製、商品名）：１４質量％、ジシアンジアミド：１．６質量％、２−エチル−４−メチル−イミダゾール：０．２質量％、ジメチルホルムアミド：７．１質量％、メチルセロソルブ：７．１質量％
Hereinafter, the present invention will be described in detail with reference to examples.
The physical property of the glass cloth in an Example and a comparative example, the preparation method of the film-form board | substrate using a glass cloth, and the test method were measured with the following method.
1. Method for measuring physical properties of glass cloth:
It measured according to JIS R3420.
2. Method for measuring the amount of bending of glass cloth:
In a 100 m long glass cloth, the amount of bending at 10 locations was measured every 10 m, and the average amount of bending was determined.
3. How to create a prepreg:
The epoxy resin varnish adjusted with the following preparation ratio was immersed in the glass cloth, the excess resin varnish was scraped off with a slit twice the thickness of each glass cloth, and dried at 170 ° C. for 3 minutes to obtain a prepreg.
[Epoxy resin varnish preparation ratio] 5046B80 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): 70% by mass, 180S75B70 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): 14% by mass, dicyandiamide: 1.6% by mass, 2 -Ethyl-4-methyl-imidazole: 0.2 mass%, dimethylformamide: 7.1 mass%, methyl cellosolve: 7.1 mass%
４．フィルム状基板の成形条件：
上記３で作成したプリプレグ（３４０ｍｍ角にカットしたもの）を用いて、両面に１２μｍ銅箔を配置し、１７５℃、３．９ＭＰａで、１時間加熱成型し、硬化させて寸法安定性評価用１プライ板のフィルム状基板を得た。
５．寸法変化率のばらつきの測定：
上述のフィルム状基板に１２５ｍｍ間隔で、タテ糸方向３箇所×ヨコ糸方向３箇所の合計９箇所の標点をつけ、タテ糸方向、ヨコ糸方向のそれぞれについて、隣接する２標点の標点間隔６箇所を測定した（測定値ａ）。次にエッチング処理により銅箔を除去し、１７０℃で３０分加熱した後、該標点間隔を再度測定した（測定値ｂ）。測定値ａと測定値ｂの差の測定値ａに対する割合（％）を寸法変化率とし、その各方向の６箇所の寸法変化率より、タテ糸方向、ヨコ糸方向それぞれの寸法変化率のバラツキ（標準偏差σn-1 ）を求めた。
4). Molding conditions for film substrate:
Using the prepreg prepared in 3 above (cut to 340 mm square), 12 μm copper foil is placed on both sides, heat molded at 175 ° C., 3.9 MPa for 1 hour, cured, and cured for dimensional stability evaluation 1 A film-like substrate of a ply plate was obtained.
5. Measurement of variation in dimensional change rate:
The above-mentioned film-like substrate is marked with a total of nine marks, 3 in the warp yarn direction x 3 in the warp direction, at 125 mm intervals, and 2 adjacent marks in the warp and warp directions. Six locations were measured (measurement value a). Next, the copper foil was removed by etching treatment, and after heating at 170 ° C. for 30 minutes, the distance between the gauge points was measured again (measurement value b). The ratio (%) of the difference between the measured value a and the measured value b to the measured value a is defined as the dimensional change rate, and the dimensional change rate in each of the warp yarn direction and the weft yarn direction varies from the dimensional change rate at six locations in each direction. (Standard deviation σ n-1 ) was determined.
＜実施例１＞
タテ糸及びヨコ糸に平均フィラメント径４．１μｍ、フィラメント数５０本で撚り数が０．７ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸８０本／ｉｎｃｈ、ヨコ糸８０本／ｉｎｃｈの織密度で平織りのガラスクロスを製織し、得られた生機を４．９Ｎ／ｍの張力下で水中に浸漬させ、連続超音波加工開繊（振動数３８ｋＨｚ，出力４００Ｗ）を行った。その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２（東レ・ダウコーニング株式会社製）を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ１２μｍ、表面ガラス被覆率８１％、平均目曲がり量４ｍｍのガラスクロスを得た。
<Example 1>
For warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 4.1μm, 50 filaments and 0.7Z twist is used. In the air jet loom, 80 warp yarns / inch, weft yarn 80 Weaving a plain weave glass cloth with a weaving density of / inch, and immersing the resulting green machine in water under a tension of 4.9 N / m, and performing continuous ultrasonic processing opening (frequency 38 kHz, output 400 W) It was. Thereafter, the paste was subjected to high temperature desizing at 400 ° C. for 24 hours.
Subsequently, SZ6032 (manufactured by Toray Dow Corning Co., Ltd.), which is a silane coupling agent, is used as the surface treatment, and the glass cloth is immersed in the solution. A glass cloth having a surface glass coverage of 81% and an average bend amount of 4 mm was obtained.
＜実施例２＞
タテ糸及びヨコ糸に平均フィラメント径４．１μｍ、フィラメント数５０本で撚り数が０．７ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸８５本／ｉｎｃｈ、ヨコ糸８５本／ｉｎｃｈの織密度でガラスクロスを製織し、得られた生機を４．９Ｎ／ｍの張力下で高圧散水流による開繊加工（加工圧２．０ＭＰａ）を行った。その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ１２μｍ、表面ガラス被覆率８５％、平均目曲がり量３ｍｍのガラスクロスを得た。
<Example 2>
For warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 4.1μm, 50 filaments and 0.7Z twist is used. In the air jet loom, 85 warp yarns / inch, weft yarn 85 A glass cloth was woven at a weaving density of 1 inch, and the resulting green machine was subjected to fiber opening processing (processing pressure 2.0 MPa) with a high-pressure water spray under a tension of 4.9 N / m. Thereafter, the paste was subjected to high temperature desizing at 400 ° C. for 24 hours.
Subsequently, SZ6032, which is a silane coupling agent, is used as a surface treatment, and a glass cloth is immersed in the solution. After drawing, the glass is dried at 120 ° C. for 1 minute, thickness 12 μm, surface glass coverage 85%, average A glass cloth having a bending amount of 3 mm was obtained.
＜実施例３＞
タテ糸及びヨコ糸に平均フィラメント径３．５μｍ、フィラメント数５０本で撚り数が０．７ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸９０本／ｉｎｃｈ、ヨコ糸９０本／ｉｎｃｈの織密度でガラスクロスを製織し、得られた生機を４．９Ｎ／ｍの張力下で高圧散水流による開繊加工（加工圧２．０ＭＰａ）を行った。その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ１０μｍ、表面ガラス被覆率８５％、平均目曲がり量５ｍｍのガラスクロスを得た。
<Example 3>
For warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 3.5μm, 50 filaments and 0.7Z twist is used. In an air jet loom, 90 warps / inch, weft 90 A glass cloth was woven at a weaving density of 1 inch, and the resulting green machine was subjected to fiber opening processing (processing pressure 2.0 MPa) with a high-pressure water spray under a tension of 4.9 N / m. Thereafter, the paste was subjected to high temperature desizing at 400 ° C. for 24 hours.
Subsequently, SZ6032, which is a silane coupling agent, is used as a surface treatment, and a glass cloth is immersed in the glass cloth. After drawing, it is dried at 120 ° C. for 1 minute, thickness 10 μm, surface glass coverage 85%, average A glass cloth having a turning amount of 5 mm was obtained.
＜実施例４＞
タテ糸及びヨコ糸に平均フィラメント径４．１μｍ、フィラメント数５０本で撚り数が０．２ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸８０本／ｉｎｃｈ、ヨコ糸８０本／ｉｎｃｈの織密度で平織りのガラスクロスを製織し、得られた生機を４．９Ｎ／ｍの張力下で高圧散水流による開繊加工（加工圧２．０ＭＰａ）を行った。その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２（東レ・ダウコーニング株式会社製）を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ１１μｍ、表面ガラス被覆率８５％、平均目曲がり量５ｍｍのガラスクロスを得た。
<Example 4>
For the warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 4.1 μm, 50 filaments and a twist number of 0.2 Z is used. In an air jet loom, 80 warp yarns / inch, weft yarn 80 A plain weave glass cloth was woven at a weaving density of 1 inch, and the resulting green machine was subjected to fiber opening processing (processing pressure 2.0 MPa) with a high-pressure water spray under a tension of 4.9 N / m. Thereafter, the paste was subjected to high temperature desizing at 400 ° C. for 24 hours.
Subsequently, SZ6032 (manufactured by Dow Corning Toray Co., Ltd.), which is a silane coupling agent, is used as a surface treatment, soaked with a glass cloth, and after squeezing, dried at 120 ° C. for 1 minute, thickness 11 μm A glass cloth having a surface glass coverage of 85% and an average bend of 5 mm was obtained.
＜比較例１＞
タテ糸及びヨコ糸に平均フィラメント径５．０μｍ、フィラメント数５０本で撚り数が１．０ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸７４本／ｉｎｃｈ、ヨコ糸７４本／ｉｎｃｈの織密度でガラスクロスを製織し、その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ２６μｍ、表面ガラス被覆率４７％、平均目曲がり量２５ｍｍのガラスクロスを得た。
<Comparative Example 1>
For the warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 5.0 μm, 50 filaments and 1.0Z twist is used. In an air jet loom, 74 warp yarns / inch, weft yarn 74 Glass cloth was woven at a weaving density of 1 book / inch, and then high-temperature de-glue at 400 ° C. for 24 hours.
Subsequently, SZ6032, which is a silane coupling agent, is used as a surface treatment, and a glass cloth is immersed in the solution. After drawing, it is dried at 120 ° C. for 1 minute, thickness 26 μm, surface glass coverage 47%, average A glass cloth having a bent amount of 25 mm was obtained.
＜比較例２＞
タテ糸及びヨコ糸に平均フィラメント径５．０μｍ、フィラメント数５０本で撚り数が１．０ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸７４本／ｉｎｃｈ、ヨコ糸７４本／ｉｎｃｈの織密度でガラスクロスを製織し、得られた生機を４．９Ｎ／ｍの張力下で高圧散水流による開繊加工（加工圧２．０ＭＰａ）を行った。その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ１８μｍ、表面ガラス被覆率８１％、平均目曲がり量１６ｍｍのガラスクロスを得た。
<Comparative example 2>
For the warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 5.0 μm, 50 filaments and 1.0Z twist is used. In an air jet loom, 74 warp yarns / inch, weft yarn 74 A glass cloth was woven at a weaving density of 1 inch, and the resulting green machine was subjected to fiber opening processing (processing pressure 2.0 MPa) with a high-pressure water spray under a tension of 4.9 N / m. Thereafter, the paste was subjected to high temperature desizing at 400 ° C. for 24 hours.
Subsequently, SZ6032, which is a silane coupling agent, is used as a surface treatment, and a glass cloth is immersed in the surface, and after drawing, dried at 120 ° C. for 1 minute, thickness 18 μm, surface glass coverage 81%, average A glass cloth having an amount of bending of 16 mm was obtained.
＜比較例３＞
タテ糸及びヨコ糸に平均フィラメント径４．１μｍ、フィラメント数１００本で撚り数が０．７ＺのＥガラス組成のガラス糸を使用し、エアージェットルームで、タテ糸４８本／ｉｎｃｈ、ヨコ糸４８本／ｉｎｃｈの織密度で平織りのガラスクロスを製織し、得られた生機を４．９Ｎ／ｍの張力下で高圧散水流による開繊加工（加工圧２．０ＭＰａ）を行った。その後４００℃で２４時間高温脱糊した。
続いて、表面処理としてシランカップリング剤であるＳＺ６０３２（東レ・ダウコーニング株式会社製）を用いて処理液とし、ガラスクロスを浸漬し、絞液後、１２０℃で１分乾燥し、厚さ２２μｍ、表面ガラス被覆率３５％、平均目曲がり量２０ｍｍのガラスクロスを得た。
以上の実施例１〜４、及び比較例１〜３のガラスクロスを用いて得たフィルム状基板の厚さ（μｍ）と上記５．の測定結果は次の表１に示されている。
<Comparative Example 3>
For warp and weft yarns, glass yarn of E glass composition with an average filament diameter of 4.1μm, 100 filaments and 0.7Z twist is used. In the air jet loom, warp yarns 48 / inch, weft yarn 48 A plain weave glass cloth was woven at a weaving density of 1 inch, and the resulting green machine was subjected to fiber opening processing (processing pressure 2.0 MPa) with a high-pressure water spray under a tension of 4.9 N / m. Thereafter, the paste was subjected to high temperature desizing at 400 ° C. for 24 hours.
Subsequently, SZ6032 (manufactured by Dow Corning Toray Co., Ltd.), which is a silane coupling agent, is used as a surface treatment, soaked in a glass cloth, and after drawing, dried at 120 ° C. for 1 minute, thickness 22 μm A glass cloth having a surface glass coverage of 35% and an average bend of 20 mm was obtained.
The thickness (μm) of the film-like substrate obtained by using the glass cloths of Examples 1 to 4 and Comparative Examples 1 to 3 and the above 5. The measurement results are shown in Table 1 below.
本発明のガラスクロス、プリプレグ、及びフィルム状基板は、プリント配線板の分野で好適に利用できる。 The glass cloth, prepreg, and film substrate of the present invention can be suitably used in the field of printed wiring boards.
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