JP2005281889A - Surface-treated glass cloth - Google Patents
Surface-treated glass cloth Download PDFInfo
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- JP2005281889A JP2005281889A JP2004095350A JP2004095350A JP2005281889A JP 2005281889 A JP2005281889 A JP 2005281889A JP 2004095350 A JP2004095350 A JP 2004095350A JP 2004095350 A JP2004095350 A JP 2004095350A JP 2005281889 A JP2005281889 A JP 2005281889A
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- silane coupling
- coupling agent
- glass
- glass cloth
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- 239000011521 glass Substances 0.000 title claims abstract description 161
- 239000004744 fabric Substances 0.000 title claims abstract description 82
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 90
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000009941 weaving Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 17
- 125000003277 amino group Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims 2
- 230000008021 deposition Effects 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000009990 desizing Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 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
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 (vinylbenzyl) aminoethyl Chemical group 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- 238000005238 degreasing 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
- 230000000694 effects Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (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ものである。 The present invention relates to a glass cloth used for a printed wiring board used in the electronic / electric field.
現在、電子機器のモバイル化、デジタル化に伴う小型化により、使用されるプリント配線板において、回路配線の細線化、小径化、高密度化が著しく進行している。このプリント配線板の絶縁材料としては、ガラスクロスをエポキシ樹脂等の熱硬化性樹脂（以下、「マトリックス樹脂」という。）に含浸させて得られるプリプレグを積層して加熱加圧硬化させた積層板が広く使用されているが、高密度化に伴い絶縁信頼性低下の問題が顕在化してきている。特に、回路配線を構成する銅等の金属が、高湿度下でイオンマイグレーションを起こし、絶縁不良が発生することがあるという問題が指摘されている。イオンマイグレーションとは、金属がイオン化し電位差によって移動する現象であるが、一般にガラスクロスとマトリックス樹脂との界面（以下、単に「界面」ともいう。）で発生することが指摘されている。
これまでにも、界面を改良してイオンマイグレーションの発生を抑制し、絶縁信頼性を改良するための提案は種々なされている。例えば、特殊なシランカップリング剤を用いること（特許文献１参照）、ガラスクロス表面にイオン交換体を導入すること（特許文献２参照）、及びガラスクロスに加湿処理を施すこと（特許文献３参照）等が提案されている。しかし、これらにおいても絶縁信頼性の改良は、未だ十分ではない。
At present, with the downsizing of electronic devices due to mobile and digitalization, circuit wiring is becoming thinner, smaller in diameter and higher in density in printed wiring boards used. As an insulating material of this printed wiring board, a laminated board obtained by laminating a prepreg obtained by impregnating a glass cloth with a thermosetting resin such as an epoxy resin (hereinafter referred to as “matrix resin”) and curing by heating and pressing. Is widely used, but the problem of lowering the insulation reliability has become apparent as the density increases. In particular, it has been pointed out that a metal such as copper constituting the circuit wiring may cause ion migration under high humidity to cause insulation failure. Ion migration is a phenomenon in which a metal ionizes and moves due to a potential difference, but it has been pointed out that it generally occurs at the interface between a glass cloth and a matrix resin (hereinafter also simply referred to as “interface”).
There have been various proposals for improving the insulation reliability by improving the interface to suppress the occurrence of ion migration. For example, a special silane coupling agent is used (see Patent Document 1), an ion exchanger is introduced on the surface of the glass cloth (see Patent Document 2), and the glass cloth is humidified (see Patent Document 3). ) Etc. have been proposed. However, even in these cases, the improvement in insulation reliability is still not sufficient.
本発明は、ガラスクロスとマトリックス樹脂との界面において、イオンマイグレーションが発生しにくいガラスクロス、すなわち絶縁信頼性に優れた積層板を作成することができるガラスクロス、及び該ガラスクロスの製造方法を提供することを目的とする。 The present invention provides a glass cloth in which ion migration is unlikely to occur at the interface between the glass cloth and the matrix resin, that is, a glass cloth capable of producing a laminate having excellent insulation reliability, and a method for producing the glass cloth. The purpose is to do.
本発明者らは、前記課題を解決するために検討した結果、ガラスクロスを構成するガラス糸について、ガラス糸を構成するガラスフィラメントの表面がほぼ完全にシランカップリング剤層で覆われること、及び該シランカップリング剤層ができるだけ単分子層に近いことが界面の改良に必要であるとの着想を得た。そして、該状態のシランカップリング剤層を形成するためのガラスクロスの表面処理方法を検討した結果、ガラスクロス表面に、一旦、過剰にシランカップリング剤を塗布して加熱乾燥によって付着させた後、水、あるいは水蒸気で洗浄することによって過剰に付着した該シランカップリング剤を一部除去し、ガラスクロス表面のシランカップリング剤の付着状態を最適化することにより、絶縁信頼性に優れたガラスクロスを得られることを見出し、本発明の完成に至った。 As a result of investigations to solve the above problems, the inventors of the present invention have, as to the glass yarn constituting the glass cloth, the surface of the glass filament constituting the glass yarn is almost completely covered with the silane coupling agent layer, and The idea was that the silane coupling agent layer should be as close to the monomolecular layer as possible to improve the interface. And as a result of examining the surface treatment method of the glass cloth for forming the silane coupling agent layer in this state, after the silane coupling agent was once applied excessively on the glass cloth surface and adhered by heat drying Glass with excellent insulation reliability by removing part of the silane coupling agent adhering excessively by washing with water or water vapor and optimizing the adhesion state of the silane coupling agent on the surface of the glass cloth The present inventors have found that a cloth can be obtained and have completed the present invention.
すなわち本発明の第一は、複数本のガラスフィラメントからなるガラス糸を製織してなるガラスクロスであって、ガラスクロスに下記一般式（１）で示されるシランカップリング剤を塗布し、９０〜３００℃で加熱乾燥させることによってガラスフィラメントの表面積１平方ｍ当たり１．３〜４．０×１０-5ｍｏｌの該シランカップリング剤を付着させた後、付着した該シランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり少なくとも０．３×１０-5ｍｏｌ以上除去することによって、該シランカップリング剤の付着量をガラスフィラメントの表面積１平方ｍ当たり０．８〜２．０×１０-5ｍｏｌに低下させたことを特徴とする表面処理ガラスクロスである。
Ｘ（Ｒ）3-nＳｉＹn ・・・（１）
（式中、Ｘはアミノ基または不飽和二重結合基のうち少なくとも１つを有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
That is, the first of the present invention is a glass cloth formed by weaving glass yarns composed of a plurality of glass filaments, and a silane coupling agent represented by the following general formula (1) is applied to the glass cloth, After heating and drying at 300 ° C., 1.3 to 4.0 × 10 −5 mol of the silane coupling agent per square meter of the surface area of the glass filament is adhered, and the adhered silane coupling agent is then added to the glass filament. By removing at least 0.3 × 10 −5 mol or more per square meter surface area, the amount of the silane coupling agent attached is 0.8 to 2.0 × 10 −5 mol per square meter surface area of the glass filament. It is a surface-treated glass cloth characterized by being lowered to
X (R) 3-n SiY n (1)
(In the formula, X is an organic functional group having at least one of an amino group or an unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group. , An ethyl group, or a phenyl group.)
該表面処理ガラスクロスにおいては、ガラス糸が、平均フィラメント径が２．５〜５．０μｍのガラスフィラメントからなるガラス糸であることが好ましい。また、シランカップリング剤が、下記一般式（２）で示されるシランカップリング剤Ａと下記一般式（３）で示されるシランカップリング剤Ｂとの混合物であることが好ましい。
Ｕ（Ｒ）3-nＳｉＹn ・・・（２）
（式中、Ｕはアミノ基を少なくとも２つ有し、かつ不飽和二重結合基を有さない有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
Ｖ（Ｒ）3-nＳｉＹn ・・・（３）
（式中、Ｖはアミノ基、及び不飽和二重結合基を少なくともそれぞれ１つずつ有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
In the surface-treated glass cloth, the glass yarn is preferably a glass yarn made of glass filaments having an average filament diameter of 2.5 to 5.0 μm. Moreover, it is preferable that a silane coupling agent is a mixture of the silane coupling agent A shown by the following general formula (2), and the silane coupling agent B shown by the following general formula (3).
U (R) 3-n SiY n (2)
(Wherein U is an organic functional group having at least two amino groups and no unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, R is any one of a methyl group, an ethyl group, and a phenyl group.)
V (R) 3-n SiY n (3)
(In the formula, V is an organic functional group having at least one amino group and one unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is methyl. A group, an ethyl group, or a phenyl group.)
本発明の第二は、複数本のガラスフィラメントからなるガラス糸を製織してなる表面処理ガラスクロスの製造方法であって、ガラスクロスを製織する工程、該ガラスクロスに下記一般式（１）で示されるシランカップリング剤濃度が０．２〜２．０質量％の処理液を塗布する工程、９０〜３００℃で加熱乾燥することによってガラスフィラメントの表面積１平方ｍ当たり１．３〜４．０×１０-5ｍｏｌの該シランカップリング剤を付着させる工程、水あるいは水蒸気により該ガラスクロスに塗布された該シランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり少なくとも０．３×１０-5ｍｏｌ以上除去することによって、該シランカップリング剤の付着量をガラスフィラメントの表面積１平方ｍ当たり０．８〜２．０×１０-5ｍｏｌとする工程よりなることを特徴とする表面処理ガラスクロスの製造方法の製造方法である。
Ｘ（Ｒ）3-nＳｉＹn ・・・（１）
（式中、Ｘはアミノ基、不飽和二重結合基のうち少なくとも１つを有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
The second of the present invention is a method for producing a surface-treated glass cloth formed by weaving glass yarns comprising a plurality of glass filaments, the step of weaving the glass cloth, and the glass cloth represented by the following general formula (1) A step of applying a treatment liquid having a silane coupling agent concentration of 0.2 to 2.0% by mass shown by heating and drying at 90 to 300 ° C. to 1.3 to 4.0 per square meter of the surface area of the glass filament. A step of adhering × 10 −5 mol of the silane coupling agent, the silane coupling agent applied to the glass cloth with water or water vapor at least 0.3 × 10 −5 mol per square meter of the surface area of the glass filament by removing more surface area per square m per 0.8 to 2.0 × 10 -5 m glass filaments adhesion amount of the silane coupling agent It is the step of the l is a manufacturing method of a method of manufacturing a surface treated glass cloth and said.
X (R) 3-n SiY n (1)
(In the formula, X is an organic functional group having at least one of an amino group and an unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group. , An ethyl group, or a phenyl group.)
該表面処理ガラスクロスの製造方法においては、シランカップリング剤として、下記一般式（２）で示されるシランカップリング剤Ａと下記一般式（３）で示されるシランカップリング剤Ｂとの混合物を用い、処理液中の該シランカップリング剤Ｂに対する該シランカップリング剤Ａの濃度がモル比で０．１以上１０以下であることが好ましい。
Ｕ（Ｒ）3-nＳｉＹn ・・・（２）
（式中、Ｕはアミノ基を少なくとも１つ有し、かつ不飽和二重結合基を有さない有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
Ｖ（Ｒ）3-nＳｉＹn ・・・（３）
（式中、Ｖはアミノ基、及び不飽和二重結合基を少なくともそれぞれ１つずつ有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
In the method for producing the surface-treated glass cloth, a mixture of a silane coupling agent A represented by the following general formula (2) and a silane coupling agent B represented by the following general formula (3) is used as the silane coupling agent. The concentration of the silane coupling agent A with respect to the silane coupling agent B in the treatment liquid is preferably 0.1 to 10 in terms of molar ratio.
U (R) 3-n SiY n (2)
(Wherein U is an organic functional group having at least one amino group and no unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, R is any one of a methyl group, an ethyl group, and a phenyl group.)
V (R) 3-n SiY n (3)
(In the formula, V is an organic functional group having at least one amino group and one unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is methyl. A group, an ethyl group, or a phenyl group.)
本発明の表面処理ガラスクロスを用いることにより、イオンマイグレーションが発生しにくい、絶縁信頼性に優れた積層板を作成することができる。 By using the surface-treated glass cloth of the present invention, it is possible to produce a laminated plate that is less prone to ion migration and excellent in insulation reliability.
本発明について、以下具体的に説明する。
（Ａ）ガラスクロス
本発明の表面処理ガラスクロスにおいては、平均フィラメント径が２．５〜５．０μｍのガラスフィラメントからなるガラス糸を製織してなるガラスクロスを好ましく使用することができる。なぜなら、平均フィラメント径５．０μｍ以下の場合、ガラス糸１本１本を構成するガラスフィラメントの本数が多くなり、且つマトリックス樹脂と接するガラスの有効表面積が大きいため、本発明の表面処理法を適用した効果がより顕著に現れるからである。
ガラスクロスを構成する経糸及び緯糸の打ち込み密度は、１０〜１００本／２５ｍｍの範囲のものが好ましく、３０〜８０本／２５ｍｍがより好ましい。また、布重量（目付け）は１５〜１１０ｇ／ｍ2 の範囲のものが好ましく、１５〜９０ｇ／ｍ2 のものがより好ましい。
織り構造については平織り構造が好ましいが、ななこ織り、朱子織り、綾織り、等の織り構造を有するガラスクロスでもよい。
積層板に使用されるガラスクロスには、通常Ｅガラス（無アルカリガラス）と呼ばれるガラスが使用されるが、本発明の表面処理ガラスクロスにおいては、Ｄガラス、Ｓガラス、高誘電率ガラス等を使用してもよい。安価であるという点からは、Ｅガラスが最も好適に使用される。
The present invention will be specifically described below.
(A) Glass cloth In the surface treatment glass cloth of this invention, the glass cloth formed by weaving the glass yarn which consists of a glass filament whose average filament diameter is 2.5-5.0 micrometers can be used preferably. This is because when the average filament diameter is 5.0 μm or less, the number of glass filaments constituting each glass yarn increases and the effective surface area of the glass in contact with the matrix resin is large, so the surface treatment method of the present invention is applied. This is because the effect is more prominent.
The driving density of the warp and weft constituting the glass cloth is preferably in the range of 10 to 100 pieces / 25 mm, and more preferably 30 to 80 pieces / 25 mm. Further, fabric weight (basis weight) is preferably in the range of 15~110g / m 2, more preferably from 15~90g / m 2.
The weave structure is preferably a plain weave structure, but may be a glass cloth having a weave structure such as Nanako weave, satin weave or twill weave.
For the glass cloth used for the laminate, glass called E glass (non-alkali glass) is usually used. In the surface-treated glass cloth of the present invention, D glass, S glass, high dielectric constant glass, etc. May be used. From the viewpoint of being inexpensive, E glass is most preferably used.
（Ｂ）シランカップリング剤
本発明の表面処理ガラスクロスにおいては、下記の一般式（１）で示されるシランカップリング剤を使用することが好ましい。また、本発明の表面処理ガラスクロスの製造方法においては、ガラスクロスにシランカップリング剤を塗布する際には、シランカップリング剤を溶媒に溶解、又は分散させた処理液（以下、単に「処理液」という。）で処理する方法が好ましい。
Ｘ（Ｒ）3-nＳｉＹn ・・・（１）
（式中、Ｘはアミノ基、不飽和二重結合基のうち少なくとも１つを有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
上記のアルコキシ基としては、何れの形態も使用できるが、ガラスクロスへの安定処理化のためには、炭素数５以下のアルコキシ基が好ましい。
(B) Silane coupling agent In the surface treatment glass cloth of this invention, it is preferable to use the silane coupling agent shown by following General formula (1). Further, in the method for producing a surface-treated glass cloth of the present invention, when a silane coupling agent is applied to the glass cloth, a treatment liquid in which the silane coupling agent is dissolved or dispersed in a solvent (hereinafter simply referred to as “treatment”). The method of processing with a liquid ") is preferable.
X (R) 3-n SiY n (1)
(In the formula, X is an organic functional group having at least one of an amino group and an unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group. , An ethyl group, or a phenyl group.)
Any form can be used as the alkoxy group, but an alkoxy group having 5 or less carbon atoms is preferable for stabilizing the glass cloth.
具体的に使用できるシランカップリング剤としては、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルメチルジメトキシシラン及びその塩酸塩、Ｎ−β−（Ｎ−ジ（ビニルベンジル）アミノエチル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩、Ｎ−β−（Ｎ−ジ（ビニルベンジル）アミノエチル）−Ｎ−γ−（Ｎ−ビニルベンジル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩、アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン等の公知の単体、又はこれらの混合物が例示できる。 Specific examples of silane coupling agents that can be used include N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride, N-β- (N-vinylbenzylaminoethyl)- γ-aminopropylmethyldimethoxysilane and its hydrochloride, N-β- (N-di (vinylbenzyl) aminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride, N-β- (N-di (vinyl) Known simple substances such as benzyl) aminoethyl) -N-γ- (N-vinylbenzyl) -γ-aminopropyltrimethoxysilane and its hydrochloride, aminopropyltrimethoxysilane, vinyltrimethoxysilane, or a mixture thereof. It can be illustrated.
上記混合物としては、下記一般式（２）で示されるシランカップリング剤Ａと下記一般式（３）で示されるシランカップリング剤Ｂとの混合物が好ましい。また、該混合物の処理液においては、該処理液中のシランカップリング剤Ｂに対するシランカップリング剤Ａの濃度がモル比で０．１以上１０以下であることが好ましい。
Ｕ（Ｒ）3-nＳｉＹn ・・・（２）
（式中、Ｕはアミノ基を少なくとも１つ有し、かつ不飽和二重結合基を有さない有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
Ｖ（Ｒ）3-nＳｉＹn ・・・（３）
（式中、Ｖはアミノ基、及び不飽和二重結合基を少なくともそれぞれ１つずつ有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
As the mixture, a mixture of a silane coupling agent A represented by the following general formula (2) and a silane coupling agent B represented by the following general formula (3) is preferable. In the treatment liquid of the mixture, the concentration of the silane coupling agent A with respect to the silane coupling agent B in the treatment liquid is preferably 0.1 to 10 in terms of molar ratio.
U (R) 3-n SiY n (2)
(Wherein U is an organic functional group having at least one amino group and no unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, R is any one of a methyl group, an ethyl group, and a phenyl group.)
V (R) 3-n SiY n (3)
(In the formula, V is an organic functional group having at least one amino group and one unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is methyl. A group, an ethyl group, or a phenyl group.)
上記のモル比の混合物の処理液をガラスクロスに塗付することにより、シランカップリング剤層の形成し易さと、複数のガラスフィラメントからなるガラス糸の開繊し易さとのバランスをとることが容易になる。該モル比が０．１未満である場合には、加熱乾燥時にシランカップリング剤同士の縮合が生じやすくなり、後工程でのガラス糸の開繊が困難になることがある。開繊が不十分であると、マトリックス樹脂の含浸時にボイドが生じ易くなるため絶縁信頼性に劣ることがあるので好ましくない。一方、該モル比が１０を超える場合には、水あるいは水蒸気により過剰なシランカップリング剤を除去する工程において、シランカップリング剤の脱落が多くなり、本発明で必要とされる量のシランカップリング剤の層を形成することが困難になることがある。 By applying the treatment liquid of the mixture having the above molar ratio to the glass cloth, it is possible to balance the ease of forming the silane coupling agent layer and the ease of opening the glass yarn composed of a plurality of glass filaments. It becomes easy. When the molar ratio is less than 0.1, condensation between silane coupling agents tends to occur during heating and drying, and it may be difficult to open the glass yarn in the subsequent step. Insufficient opening is not preferable because voids are likely to occur when the matrix resin is impregnated, resulting in poor insulation reliability. On the other hand, when the molar ratio exceeds 10, in the step of removing excess silane coupling agent with water or water vapor, the silane coupling agent drops off, and the amount of silane cup required by the present invention. It may be difficult to form a layer of ring agent.
（Ｃ）ガラスクロスの表面処理
処理液の溶媒としては、水、又は有機溶媒の何れも使用できるが、安全性、地球環境保護の観点から、水を主溶媒とすることが好ましい。水を主溶媒とした処理液を得る方法としては、シランカップリング剤を直接水に投入する方法、シランカップリング剤を水溶性有機溶媒に溶解させて有機溶媒溶液とした後に該有機溶媒溶液を水に投入する方法、の何れかの方法が好ましい。また、シランカップリング剤の処理液中での水分散性、安定性を向上させるために、界面活性剤を併用することも可能である。
複数本のガラスフィラメントからなるガラス糸を製織してなるガラスクロスにおいて、各ガラスフィラメントの表面をほぼ完全にシランカップリング剤からなる層で覆うためには、１．反応場内のシランカップリング剤量を増やす方法、２．シランカップリング剤とガラスフィラメント表面の反応時間を長くする方法、等が考えられる。具体的には、１．では処理液中のシランカップリング剤濃度を高くする方法、２．ではガラスクロスを処理液中へ含浸させる時間を長くする方法、または処理液中へ含浸させる回数を２回以上に増やす方法が挙げられる。
(C) Surface treatment of glass cloth As the solvent of the treatment liquid, either water or an organic solvent can be used, but water is preferably used as the main solvent from the viewpoint of safety and protection of the global environment. As a method for obtaining a treatment liquid containing water as a main solvent, a method in which a silane coupling agent is directly added to water, an organic solvent solution is prepared by dissolving the silane coupling agent in a water-soluble organic solvent, and then the organic solvent solution is used. Any one of the methods of adding to water is preferable. In order to improve the water dispersibility and stability of the silane coupling agent in the treatment liquid, it is also possible to use a surfactant in combination.
In order to cover the surface of each glass filament almost completely with a layer made of a silane coupling agent in a glass cloth formed by weaving glass yarns made of a plurality of glass filaments, 1. a method for increasing the amount of silane coupling agent in the reaction field; A method of increasing the reaction time between the silane coupling agent and the glass filament surface is conceivable. Specifically, Then, a method for increasing the concentration of the silane coupling agent in the treatment liquid; 2. Then, a method of increasing the time for impregnating the glass cloth into the treatment liquid or a method of increasing the number of times of impregnation into the treatment liquid to 2 times or more can be mentioned.
本発明の表面処理ガラスクロスでの製造方法においては、まず１．ないし２．の方法によってガラスフィラメントの表面積１平方ｍ当たり１．３〜４．０×１０-5ｍｏｌのシランカップリング剤を塗布することにより、ほぼ完全にガラスフィラメントの表面を覆うのに必要な量より過剰量のシランカップリング剤を、加熱乾燥によりガラス表面に固着させる。次に、洗浄により該過剰量のシランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり少なくとも０．３×１０-5ｍｏｌ以上除去し、付着量をガラスフィラメントの表面積１平方ｍ当たり０．８〜２．０×１０-5ｍｏｌの範囲になるようにする。こうすることにより、ガラス糸を構成するガラスフィラメント１本１本の表面全体に、ほぼ完全、かつ均一にシランカップリング剤層を形成することができると考えられる。 In the production method of the surface-treated glass cloth of the present invention, first, 1. Or 2. By applying 1.3 to 4.0 × 10 −5 mol of the silane coupling agent per square meter of the surface area of the glass filament by the above method, the amount necessary to almost completely cover the surface of the glass filament is exceeded. An amount of silane coupling agent is fixed to the glass surface by heat drying. Next, the excess amount of the silane coupling agent is removed by washing at least 0.3 × 10 −5 mol or more per square meter of the surface area of the glass filament, and the adhesion amount is 0.8 to 0.8 per square meter of the surface area of the glass filament. The range is 2.0 × 10 −5 mol. By doing so, it is considered that a silane coupling agent layer can be formed almost completely and uniformly on the entire surface of each glass filament constituting the glass yarn.
該付着量が０．８×１０-5ｍｏｌ未満の場合には、絶縁信頼性試験を行った場合に、マトリックス樹脂とガラスフィラメント表面の界面で吸水が生じることが原因と考えられる界面剥離による白化現象が俄かに発生するようになり、絶縁信頼性に劣る。一方、該付着量が２．０×１０-5ｍｏｌを超える場合には、シランカップリング剤同士の縮合層の形成に起因すると考えられる吸水が生じ、かつガラス糸束内にボイドが生じ、やはり絶縁信頼性に劣る。
処理液中のシランカップリング剤の濃度は、ガラスフィラメントの表面積１平方ｍ当たりに対してシランカップリング剤を１．３〜４．０×１０-5ｍｏｌ塗布する必要があることから、シランカップリング剤が０．２質量％以上、２．０質量％以下で選定されるのが好ましい。
When the adhesion amount is less than 0.8 × 10 −5 mol, whitening due to interface peeling, which is considered to be caused by water absorption at the interface between the matrix resin and the glass filament surface, is performed when an insulation reliability test is performed. Phenomenon occurs far and the insulation reliability is poor. On the other hand, when the adhesion amount exceeds 2.0 × 10 −5 mol, water absorption is considered to be caused by the formation of a condensation layer between the silane coupling agents, and voids are generated in the glass yarn bundle. Insulation reliability is poor.
Since the concentration of the silane coupling agent in the treatment liquid needs to be 1.3 to 4.0 × 10 −5 mol of the silane coupling agent per 1 square meter of the surface area of the glass filament, It is preferable that the ring agent is selected in an amount of 0.2% by mass or more and 2.0% by mass or less.
処理液をガラスクロスに塗布する方法としては、（ア）処理液をバスに溜め、ガラスクロスを浸漬、通過させる方法（以下、「浸漬法」という。）、（イ）ロールコーター、ダイコーター、またはグラビアコーター等で処理液をガラスクロスに直接塗布する方法、等が可能である。上記（ア）の浸漬法にて塗布する場合は、ガラスクロスの処理液への浸漬時間を０．５秒以上、１分以下に選定するのが望ましい。
また、ガラスクロスに処理液を塗布した後、溶媒を加熱乾燥させる方法としては、熱風、電磁波等公知の方法が可能である。加熱乾燥温度は、シランカップリング剤とガラスとの反応が十分に行われるように、９０℃以上が好ましく、１００℃以上であればより好ましい。また、シランカップリング剤が有する有機官能基の劣化を防ぐために、３００℃以下が好ましく、２００℃以下であればより好ましい。
As a method of applying the treatment liquid to the glass cloth, (a) a method of storing the treatment liquid in a bath and immersing and passing the glass cloth (hereinafter referred to as “immersion method”), (b) a roll coater, a die coater, Or the method of apply | coating a process liquid directly to a glass cloth with a gravure coater etc. is possible. In the case of applying by the above-mentioned dipping method (a), it is desirable to select the dipping time of the glass cloth in the treatment liquid to be 0.5 second or more and 1 minute or less.
In addition, as a method of heating and drying the solvent after applying the treatment liquid to the glass cloth, known methods such as hot air and electromagnetic waves can be used. The heating and drying temperature is preferably 90 ° C. or higher, and more preferably 100 ° C. or higher so that the reaction between the silane coupling agent and glass is sufficiently performed. Moreover, in order to prevent deterioration of the organic functional group which a silane coupling agent has, 300 degrees C or less is preferable, and if it is 200 degrees C or less, it is more preferable.
表面処理ガラスクロスの過剰なシランカップリング剤を除去する方法としては、洗浄液、又は蒸気（以下、一括して「洗浄液」という。）で洗浄する方法が好ましい。該洗浄液としては水、あるいは水蒸気が好ましい。具体的な洗浄の方法としては、高圧柱状流、高圧ウォータージェット、高圧蒸気等、公知の方法が適用可能であり、開繊加工を兼ねて実施することが好ましい。なお、参考までに、代表的スタイルを有する本発明の表面処理ガラスクロスについて、通常使用される強熱減量値で測定した、洗浄前後におけるシランカップリング剤の付着量を表１に示す。 As a method of removing the excess silane coupling agent from the surface-treated glass cloth, a method of cleaning with a cleaning liquid or steam (hereinafter collectively referred to as “cleaning liquid”) is preferable. The cleaning liquid is preferably water or water vapor. As a specific cleaning method, a known method such as a high-pressure columnar flow, a high-pressure water jet, or a high-pressure steam can be applied, and it is preferable that the cleaning is also performed. For reference, Table 1 shows the adhesion amount of the silane coupling agent before and after cleaning, which was measured with a commonly used ignition loss value for the surface-treated glass cloth of the present invention having a typical style.
次に実施例、比較例によって本発明をさらに詳細に説明する。なお、ガラスフィラメントの表面積１平方ｍ当たりのシランカップリング剤の付着量を求めるにあたって、ガラスクロス１平方ｍ当たりのガラスフィラメントの表面積は以下のように計算した。なお、平均フィラメント径とはフィラメントの平均直径を意味し、目付とは加熱脱脂後のガラスクロス１ｍ2 当たりの質量（ｇ）をいい、Ｔｅｘとは収束剤を除いたガラス糸１ｋｍ当たりの質量（ｇ）をいう。
表面積（ｍ2 ）＝（ガラス糸１本を構成するフィラメント本数（本））×（平均フィラメント径（μｍ）×１０-6）×円周率×（目付（ｇ））÷（Ｔｅｘ×１０-3）
Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, when calculating | requiring the adhesion amount of the silane coupling agent per square meter surface area of a glass filament, the surface area of the glass filament per square meter of glass cloth was computed as follows. The average filament diameter means the average diameter of the filament, the basis weight means the mass (g) per 1 m 2 of the glass cloth after heat degreasing, and Tex is the mass per 1 km of the glass yarn excluding the sizing agent ( g).
Surface area (m 2 ) = (number of filaments constituting one glass yarn (number)) × (average filament diameter (μm) × 10 −6 ) × circumferential rate × (weight per unit (g)) ÷ (Tex × 10 − 3 )
（実施例１）
加熱脱糊後のガラスクロス（旭シュエーベル社製スタイル１０８０：平均フィラメント径５μｍ、使用するガラス糸は１本あたりのフィラメント本数２０４本でＴｅｘ１１ｇ／ｋｍ、経糸の打ち込み密度６０本／２５ｍｍ 緯糸の打ち込み密度４７本／２５ｍｍ 目付４８ｇ／ｍ2 ）を、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランの塩酸塩（東レダウコーニング株式会社製；ＳＺ６０３２）、及び酢酸、界面活性剤を、それぞれ１５ｇ、２ｇ、０．２ｇずつ水１リットルに分散させた処理液に２秒間浸漬し、１７０℃で１分間加熱乾燥することによって、シランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり２．０１×１０-5ｍｏｌ付着させた。次に圧力２．０ＭＰａの高圧柱状流水により２秒間洗浄して過剰なシランカップリング剤の一部を除去して、ガラスフィラメントの表面積１平方ｍ当たり１．０５×１０-5ｍｏｌのシランカップリング剤が付着した表面処理ガラスクロスを得た。
(Example 1)
Glass cloth after heat desizing (Asahi Schavel style 1080: average filament diameter of 5 μm, glass filament used is 204 filaments per thread, Tex 11 g / km, warp drive density 60 threads / 25 mm Weft drive density 47/25 mm per unit weight 48 g / m 2 ), N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (manufactured by Toray Dow Corning Co., Ltd .; SZ6032), acetic acid, interface The silane coupling agent is immersed in a treatment solution in which 15 g, 2 g, and 0.2 g of water are dispersed in 1 liter of water for 2 seconds, and heated and dried at 170 ° C. for 1 minute. 2.01 × 10 −5 mol per m was deposited. Next, it was washed with high-pressure columnar running water having a pressure of 2.0 MPa for 2 seconds to remove a part of the excess silane coupling agent, and 1.05 × 10 −5 mol of silane coupling per square meter of the surface area of the glass filament. A surface-treated glass cloth with an agent attached thereto was obtained.
（実施例２）
実施例１と同一の加熱脱糊後のガラスクロスを、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランの塩酸塩（東レダウコーニング株式会社製；ＳＺ６０３２）、Ｎ−β−（Ｎ−ベンジルアミノエチルアミノプロピル）トリメトキシシランの塩酸塩（信越化学株式会社製；ＫＢＭ６１２３）、酢酸、界面活性剤を、それぞれ１５ｇ、５ｇ、２ｇ、０．２ｇずつ水１リットルに分散させた処理液に２秒間浸漬し、１７０℃で１分間加熱乾燥することによって、シランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり合計で２．０８×１０-5ｍｏｌ付着させた。次に、実施例１と同様に高圧柱状流水により洗浄し、ガラスフィラメントの表面積１平方ｍ当たり０．９５×１０-5ｍｏｌのシランカップリング剤が付着した表面処理ガラスクロスを得た。
(Example 2)
The glass cloth after the same heat desizing as in Example 1 was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (manufactured by Toray Dow Corning Co., Ltd .; SZ6032), N -Β- (N-benzylaminoethylaminopropyl) trimethoxysilane hydrochloride (manufactured by Shin-Etsu Chemical Co., Ltd .; KBM6123), acetic acid, and surfactant were added to 1 liter of water in an amount of 15 g, 5 g, 2 g, and 0.2 g, respectively. A total of 2.08 × 10 −5 mol of the silane coupling agent was adhered per square meter of the surface area of the glass filament by immersing in the dispersed treatment solution for 2 seconds and heating and drying at 170 ° C. for 1 minute. Next, it was washed with high-pressure columnar running water in the same manner as in Example 1 to obtain a surface-treated glass cloth with 0.95 × 10 −5 mol of a silane coupling agent attached per square meter of surface area of the glass filament.
（実施例３）
実施例１と同一の加熱脱糊後のガラスクロスを、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランの塩酸塩（東レダウコーニング株式会社製；ＳＺ６０３２）、酢酸、界面活性剤を、それぞれ６ｇ、１ｇ、０．２ｇずつ水１リットルに分散させた処理液に２秒間浸漬し１７０℃で１分間加熱乾燥することを２回繰り返し、シランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり１．７０×１０-5ｍｏｌ付着させた。次に、実施例１と同様に高圧柱状流水により洗浄し、ガラスフィラメントの表面積１平方ｍ当たり１．１０×１０-5ｍｏｌのシランカップリング剤が付着した表面処理ガラスクロスを得た。
(Example 3)
The glass cloth after the same heat desizing as in Example 1 was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (manufactured by Toray Dow Corning Co., Ltd .; SZ6032), acetic acid. The surfactant was soaked in a treatment solution in which 6 g, 1 g, and 0.2 g of each were dispersed in 1 liter of water for 2 seconds and heat-dried at 170 ° C. for 1 minute twice, and the silane coupling agent was added to the glass filament. Of 1.70 × 10 −5 mol per square meter of surface area. Next, it was washed with high-pressure columnar running water in the same manner as in Example 1 to obtain a surface-treated glass cloth with 1.10 × 10 −5 mol of a silane coupling agent adhered per square meter of the surface area of the glass filament.
（比較例１）
実施例１と同一の加熱脱糊後のガラスクロスを、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランの塩酸塩（東レダウコーニング株式会社製；ＳＺ６０３２）、酢酸、界面活性剤を、それぞれ６ｇ、１ｇ、０．２ｇずつ水１リットルに分散させた処理液に２秒間浸漬し、１７０℃で１分間加熱乾燥することによって、シランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり０．９１×１０-5ｍｏｌ付着させた。次に、実施例１と同様に高圧柱状流水により洗浄し、ガラスフィラメントの表面積１平方ｍ当たり０．７１×１０-5ｍｏｌのシランカップリング剤が付着した表面処理ガラスクロスを得た。
(Comparative Example 1)
The glass cloth after the same heat desizing as in Example 1 was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (manufactured by Toray Dow Corning Co., Ltd .; SZ6032), acetic acid. The surface-active agent was immersed in a treatment solution in which 6 g, 1 g, and 0.2 g of water were dispersed in 1 liter of water for 2 seconds and dried by heating at 170 ° C. for 1 minute, whereby the surface area of the glass filament was reduced. 0.91 × 10 −5 mol was deposited per square meter. Next, it was washed with high-pressure columnar running water in the same manner as in Example 1 to obtain a surface-treated glass cloth with 0.71 × 10 −5 mol of a silane coupling agent attached per square meter of surface area of the glass filament.
（比較例２）
実施例１と同一の加熱脱糊後のガラスクロスを、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランの塩酸塩（東レダウコーニング株式会社製；ＳＺ６０３２）、酢酸、界面活性剤を、それぞれ６０ｇ、１０ｇ、０．２ｇずつ水１リットルに分散させた処理液に２秒間浸漬し、１７０℃で１分間加熱乾燥することによってシランカップリング剤をガラスフィラメントの表面積１平方ｍ当たり８．４５×１０-5ｍｏｌ付着させた。次に、実施例１と同様に高圧柱状流水により洗浄し、ガラスフィラメントの表面積１平方ｍ当たり２．５２×１０-5ｍｏｌのシランカップリング剤が付着した表面処理ガラスクロスを得た。
(Comparative Example 2)
The glass cloth after the same heat desizing as in Example 1 was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (manufactured by Toray Dow Corning Co., Ltd .; SZ6032), acetic acid. The surface active agent was immersed in a treatment solution in which 60 g, 10 g, and 0.2 g of each surfactant were dispersed in 1 liter of water for 2 seconds, and dried by heating at 170 ° C. for 1 minute, whereby the surface area of the glass filament 1 8.45 × 10 −5 mol was deposited per square meter. Next, it was washed with high-pressure columnar running water in the same manner as in Example 1 to obtain a surface-treated glass cloth to which 2.52 × 10 −5 mol of a silane coupling agent was attached per square meter of surface area of the glass filament.
（比較例３）
実施例１と同一の加熱脱糊後のガラスクロスを、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランの塩酸塩（東レダウコーニング株式会社製；ＳＺ６０３２）、酢酸、界面活性剤を、それぞれ６ｇ、１ｇ、０．２ｇずつ水１リットルに分散させた処理液に２秒間浸漬した。次に、１７０℃で１分間加熱乾燥し、ガラスフィラメントの表面積１平方ｍ当たり０．９１×１０-5ｍｏｌのシランカップリング剤が付着した表面処理ガラスクロスを得た。
(Comparative Example 3)
The glass cloth after the same heat desizing as in Example 1 was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (manufactured by Toray Dow Corning Co., Ltd .; SZ6032), acetic acid. The surfactant was immersed in a treatment solution in which 6 g, 1 g, and 0.2 g, respectively, were dispersed in 1 liter of water for 2 seconds. Next, it was heated and dried at 170 ° C. for 1 minute to obtain a surface-treated glass cloth on which 0.91 × 10 −5 mol of a silane coupling agent was adhered per square meter of the surface area of the glass filament.
＜積層板の作成方法＞
上述の実施例・比較例で得た表面処理ガラスクロスに、エポキシ樹脂ワニス（低臭素化ビスフェノールＡ型エポキシ樹脂４０質量部、ｏ−クレゾール型ノボラックエポキシ樹脂１０質量部、ジメチルホルムアミド５０質量部、ジシアンジアミド１質量部、及び２−エチル−４−メチルイミダゾール０．１質量部の混合物）を含浸させ、１６０℃で２分間乾燥後プリプレグを得た。このプリプレグ４枚を重ね、さらに上下に厚さ１２μｍの銅箔を重ね、１７５℃、４０ｋｇ／ｃｍ2 で６０分間加熱加圧して積層板を得た。
<Method for creating laminated sheet>
An epoxy resin varnish (40 parts by mass of a low brominated bisphenol A type epoxy resin, 10 parts by mass of an o-cresol type novolac epoxy resin, 50 parts by mass of dimethylformamide, dicyandiamide) was applied to the surface-treated glass cloth obtained in the above-mentioned examples and comparative examples. A mixture of 1 part by mass and 0.1 part by mass of 2-ethyl-4-methylimidazole) was impregnated and dried at 160 ° C. for 2 minutes to obtain a prepreg. Four prepregs were stacked, and a copper foil having a thickness of 12 μm was stacked on top and bottom, and heated and pressed at 175 ° C. and 40 kg / cm 2 for 60 minutes to obtain a laminate.
＜ガラスフィラメント表面におけるシランカップリング剤付着量評価方法＞
表面処理ガラスクロスを約８００℃で１分間加熱し、発生した気体中の二酸化炭素量をガスクロマトグラフィーで測定し、表面処理していない加熱脱糊後のガラスクロスから発生した気体中の二酸化炭素量を差し引いて、ガラスクロス表面処理剤から発生する炭素数を求め、そのすべてがシランカップリング剤のアルコキシ基を除く有機官能基部分のみ（前述の化学式におけるＸ、Ｕ、Ｖ）に由来するものと仮定して、付着量を算出した。なお、シランカップリング剤の他に、界面活性剤、加熱乾燥時に完全に除かれなかった酢酸等が含まれている可能性があるが、微量であり、且つ水あるいは水蒸気による除去工程で脱落し易いためすべてシランカップリング剤として計算するものとする。
また、シランカップリング剤を混合物として塗布する場合には、該混合物の処理液中におけるモル比からシランカップリング剤の平均分子量を決定し、同様に付着量を算出した。
<Method for evaluating adhesion amount of silane coupling agent on glass filament surface>
The surface-treated glass cloth is heated at about 800 ° C. for 1 minute, the amount of carbon dioxide in the generated gas is measured by gas chromatography, and the carbon dioxide in the gas generated from the glass cloth after heat deglueing that is not surface-treated. Subtracting the amount to determine the number of carbon atoms generated from the glass cloth surface treatment agent, all of which are derived from only the organic functional group portion excluding the alkoxy group of the silane coupling agent (X, U, V in the above chemical formula) Assuming that, the adhesion amount was calculated. In addition to the silane coupling agent, there may be a surfactant, acetic acid that has not been completely removed at the time of heating and drying, but it is a trace amount and is removed in the removal step with water or water vapor. Since it is easy, all shall be calculated as a silane coupling agent.
Moreover, when apply | coating a silane coupling agent as a mixture, the average molecular weight of the silane coupling agent was determined from the molar ratio in the process liquid of this mixture, and the adhesion amount was computed similarly.
＜積層板の吸水率評価方法＞
積層板を、温度１２０℃湿度１００％ＲＨの雰囲気下にまず１２時間曝し重量を測定し、さらに１５０時間曝し重量を測定し、その間の重量変化から吸水率を評価した。
＜絶縁信頼性評価方法＞
積層板の両面の銅箔上に、０．２ｍｍ間隔のスルーホールを配する配線パターンを作成し、温度１２０℃湿度８５％ＲＨの雰囲気下で１０Ｖの電圧をかけ、抵抗値の変化を測定した。試験開始後５００時間以内に抵抗が１ＭΩ未満になった場合を絶縁不良とし、絶縁不良とならなかったサンプルの割合で評価した（サンプル数は１０個とした。）。
<Method for evaluating water absorption rate of laminated sheet>
The laminate was first exposed to an atmosphere of temperature 120 ° C. and humidity 100% RH for 12 hours to measure the weight, further exposed to 150 hours to measure the weight, and the water absorption was evaluated from the change in weight during that period.
<Insulation reliability evaluation method>
A wiring pattern having through-holes with a spacing of 0.2 mm was created on the copper foils on both sides of the laminate, and a change in resistance value was measured by applying a voltage of 10 V in an atmosphere at a temperature of 120 ° C. and a humidity of 85% RH. . The case where the resistance was less than 1 MΩ within 500 hours after the start of the test was regarded as an insulation failure, and the ratio of samples that did not show an insulation failure was evaluated (the number of samples was 10).
＜含浸性評価方法＞
１００ｃｍ2 のプリプレグを上から光学顕微鏡により観察し、糸束内に見えるボイドの数を数えた。
実施例１、２、３と比較例１、２、３で示した表面処理ガラスクロスを用いて作成した積層板の吸水率、及び絶縁信頼性評価結果を表２に、またプリプレグの含浸性評価結果を表３にそれぞれまとめた。
実施例１、２、３の表面処理ガラスクロスは、吸水率が比較例１、３に比べ著しく小さく、絶縁信頼性に非常に優れていることが分かった。また比較例２と比べて絶縁信頼性に優れていることが分かった。さらに、実施例２は、実施例１、３比較例１、２、３に比べボイド数が少なく、含浸性にも優れることが分かった。
<Impregnation evaluation method>
A 100 cm 2 prepreg was observed from above with an optical microscope, and the number of voids visible in the yarn bundle was counted.
Table 2 shows the water absorption rate and the insulation reliability evaluation results of the laminates prepared using the surface-treated glass cloths shown in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3, and the prepreg impregnation evaluation The results are summarized in Table 3.
It was found that the surface-treated glass cloths of Examples 1, 2, and 3 have extremely low water absorption as compared with Comparative Examples 1 and 3, and are extremely excellent in insulation reliability. Moreover, it turned out that it is excellent in insulation reliability compared with the comparative example 2. Furthermore, it was found that Example 2 had fewer voids than Examples 1 and 3 and Comparative Examples 1, 2, and 3, and was excellent in impregnation.
本発明の表面処理ガラスクロスは、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基材として好適に利用できる。 The surface-treated glass cloth of the present invention can be suitably used as a base material used for a printed wiring board used in the electronic / electric field.
Claims (5)
Ｘ（Ｒ）3-nＳｉＹn ・・・（１）
（式中、Ｘはアミノ基、不飽和二重結合基のうち少なくとも１つを有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。） A glass cloth formed by weaving glass yarns composed of a plurality of glass filaments, by applying a silane coupling agent represented by the following general formula (1) to the glass cloth and heating and drying at 90 to 300 ° C. After depositing 1.3-4.0 × 10 −5 mol of the silane coupling agent per square meter surface area of the glass filament, the deposited silane coupling agent is at least 0 per square meter surface area of the glass filament. .3 × 10 −5 mol or more is removed to reduce the adhesion amount of the silane coupling agent to 0.8 to 2.0 × 10 −5 mol per square meter of the surface area of the glass filament. Surface treated glass cloth.
X (R) 3-n SiY n (1)
(In the formula, X is an organic functional group having at least one of an amino group and an unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group. , An ethyl group, or a phenyl group.)
Ｕ（Ｒ）3-nＳｉＹn ・・・（２）
（式中、Ｕはアミノ基を少なくとも１つ有し、かつ不飽和二重結合基を有さない有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
Ｖ（Ｒ）3-nＳｉＹn ・・・（３）
（式中、Ｖはアミノ基、及び不飽和二重結合基を少なくともそれぞれ１つずつ有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。） The silane coupling agent is a mixture of a silane coupling agent A represented by the following general formula (2) and a silane coupling agent B represented by the following general formula (3). The surface treatment glass cloth as described in any one of these.
U (R) 3-n SiY n (2)
(Wherein U is an organic functional group having at least one amino group and no unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, R is any one of a methyl group, an ethyl group, and a phenyl group.)
V (R) 3-n SiY n (3)
(In the formula, V is an organic functional group having at least one amino group and one unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is methyl. A group, an ethyl group, or a phenyl group.)
Ｘ（Ｒ）3-nＳｉＹn ・・・（１）
（式中、Ｘはアミノ基、不飽和二重結合基のうち少なくとも１つを有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。） A method for producing a surface-treated glass cloth formed by weaving glass yarns comprising a plurality of glass filaments, the step of weaving the glass cloth, and the concentration of the silane coupling agent represented by the following general formula (1) in the glass cloth Is a step of applying a treatment liquid of 0.2 to 2.0% by mass, by heating and drying at 90 to 300 ° C., 1.3 to 4.0 × 10 −5 mol of the glass filament surface area per square meter A step of attaching a silane coupling agent, removing the silane coupling agent applied to the glass cloth with water or water vapor at least 0.3 × 10 −5 mol or more per square meter of the surface area of the glass filament, the step of the deposition amount of the silane coupling agent and 0.8 to 2.0 × 10 -5 mol per surface area 1 sq. m of glass filaments The method of manufacturing a surface treated glass cloth characterized by comprising.
X (R) 3-n SiY n (1)
(In the formula, X is an organic functional group having at least one of an amino group and an unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is a methyl group. , An ethyl group, or a phenyl group.)
Ｕ（Ｒ）3-nＳｉＹn ・・・（２）
（式中、Ｕはアミノ基を少なくとも１つ有し、かつ不飽和二重結合基を有さない有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。）
Ｖ（Ｒ）3-nＳｉＹn ・・・（３）
（式中、Ｖはアミノ基、及び不飽和二重結合基を少なくともそれぞれ１つずつ有する有機官能基であり、Ｙはアルコキシ基であり、ｎは１以上３以下の整数であり、Ｒはメチル基、エチル基、フェニル基のいずれかの基である。） As a silane coupling agent, a mixture of a silane coupling agent A represented by the following general formula (2) and a silane coupling agent B represented by the following general formula (3) is used, and the silane coupling agent in the treatment liquid is used. The method for producing a surface-treated glass cloth according to claim 4, wherein the concentration of the silane coupling agent A with respect to B is 0.1 to 10 in terms of molar ratio.
U (R) 3-n SiY n (2)
(Wherein U is an organic functional group having at least one amino group and no unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, R is any one of a methyl group, an ethyl group, and a phenyl group.)
V (R) 3-n SiY n (3)
(In the formula, V is an organic functional group having at least one amino group and one unsaturated double bond group, Y is an alkoxy group, n is an integer of 1 to 3, and R is methyl. A group, an ethyl group, or a phenyl group.)
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| JP4497977B2 JP4497977B2 (en) | 2010-07-07 |
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| JP2008069472A (en) * | 2006-09-13 | 2008-03-27 | Asahi Kasei Electronics Co Ltd | Water solution of glass treatment agent and surface treatment method of glass cloth |
| JP2009144255A (en) * | 2007-12-11 | 2009-07-02 | Asahi Kasei Electronics Co Ltd | Surface-treated glass cloth |
| JP2009173472A (en) * | 2008-01-22 | 2009-08-06 | Asahi Kasei E-Materials Corp | Method for producing glass filler |
| WO2011037083A1 (en) * | 2009-09-25 | 2011-03-31 | 積水化学工業株式会社 | Transparent composite sheet |
| JP2016069401A (en) * | 2014-09-26 | 2016-05-09 | 住友ベークライト株式会社 | Prepreg, resin board, metal-clad laminate, printed wiring board, and semiconductor device |
| WO2016175248A1 (en) * | 2015-04-27 | 2016-11-03 | 旭化成株式会社 | Glass cloth |
| JP2018127747A (en) * | 2017-02-10 | 2018-08-16 | 旭化成株式会社 | Glass cloth, prepreg and printed wiring board |
| WO2021131154A1 (en) * | 2019-12-26 | 2021-07-01 | 日東紡績株式会社 | Surface-treated glass cloth |
| TWI820954B (en) * | 2021-10-08 | 2023-11-01 | 日商旭化成股份有限公司 | Glass cloth, prepreg, printed wiring board, integrated circuit, and electronic equipment |
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| US10669197B2 (en) | 2014-01-14 | 2020-06-02 | Shin-Etsu Chemical Co., Ltd. | Surface-modified glass fiber film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008069472A (en) * | 2006-09-13 | 2008-03-27 | Asahi Kasei Electronics Co Ltd | Water solution of glass treatment agent and surface treatment method of glass cloth |
| JP2009144255A (en) * | 2007-12-11 | 2009-07-02 | Asahi Kasei Electronics Co Ltd | Surface-treated glass cloth |
| JP2009173472A (en) * | 2008-01-22 | 2009-08-06 | Asahi Kasei E-Materials Corp | Method for producing glass filler |
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| WO2016175248A1 (en) * | 2015-04-27 | 2016-11-03 | 旭化成株式会社 | Glass cloth |
| US20180094110A1 (en) * | 2015-04-27 | 2018-04-05 | Asahi Kasei Kabushiki Kaisha | Glass cloth |
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