JP4397260B2 - Glass cloth treatment solution for printed circuit boards - Google Patents
Glass cloth treatment solution for printed circuit boards Download PDFInfo
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- JP4397260B2 JP4397260B2 JP2004088404A JP2004088404A JP4397260B2 JP 4397260 B2 JP4397260 B2 JP 4397260B2 JP 2004088404 A JP2004088404 A JP 2004088404A JP 2004088404 A JP2004088404 A JP 2004088404A JP 4397260 B2 JP4397260 B2 JP 4397260B2
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- silane coupling
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- 239000011521 glass Substances 0.000 title claims description 109
- 239000004744 fabric Substances 0.000 title claims description 60
- 239000004094 surface-active agent Substances 0.000 claims description 100
- 239000007864 aqueous solution Substances 0.000 claims description 53
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 21
- 238000004381 surface treatment Methods 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- -1 polyoxyethylene octyl ethers Polymers 0.000 description 12
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- 150000001875 compounds Chemical class 0.000 description 9
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 229920002114 octoxynol-9 Polymers 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 229910000679 solder Inorganic materials 0.000 description 2
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- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OSSMYOQKNHMTIP-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CO[Si](C)(OC)CCC(N)CCN OSSMYOQKNHMTIP-UHFFFAOYSA-N 0.000 description 1
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011889 copper foil 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
- 238000005520 cutting process Methods 0.000 description 1
- NFCHYERDRQUCGJ-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[SiH](OC)CCCOCC1CO1 NFCHYERDRQUCGJ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Description
本発明は、電子・電気分野で使用されるプリント配線板の基材として使用されるガラスクロスとマトリックス樹脂の間の接着力を向上させるガラス処理剤水溶液、該ガラス処理剤水溶液を用いたガラスクロスの表面処理方法、及び該表面処理方法により得られたガラスクロスに関するものである。 The present invention relates to an aqueous glass treating agent solution for improving the adhesion between a glass cloth used as a substrate of a printed wiring board used in the electronic / electric field and a matrix resin, and a glass cloth using the aqueous glass treating agent solution And a glass cloth obtained by the surface treatment method.
プリント配線板には、マトリックス樹脂を含浸し、保持し、強度を保つ基材として、その優れた耐熱性、寸法安定性、電気絶縁性等の特性からガラスクロスが主として用いられている。ガラスクロス表面上には、無機物質であるガラスクロスと有機物質である樹脂との親和性を高めるために、ガラスとマトリックス樹脂との両方に反応性を有する化合物、いわゆるシランカップリング剤により処理されている。シランカップリング剤によるガラスクロスの表面処理は、一般的には、シランカップリング剤の水溶液（以下、「ガラス処理剤水溶液」ともいう。）中にガラスクロスを浸漬し、乾燥させて水分を除去することで行われる。該表面処理においては、ガラス処理剤水溶液中でシラノール化したシランカップリング剤が乾燥段階でガラスと縮合し、ガラスとシランカップリング剤が結合する。 In the printed wiring board, a glass cloth is mainly used as a base material impregnated with a matrix resin, retained, and maintained in strength because of its excellent heat resistance, dimensional stability, electrical insulation and the like. The glass cloth surface is treated with a compound reactive to both glass and matrix resin, so-called silane coupling agent, in order to increase the affinity between glass cloth, which is an inorganic substance, and resin, which is an organic substance. ing. Surface treatment of glass cloth with a silane coupling agent is generally performed by immersing the glass cloth in an aqueous solution of a silane coupling agent (hereinafter also referred to as “glass treatment agent aqueous solution”) and drying to remove moisture. It is done by doing. In the surface treatment, the silane coupling agent silanolated in the glass treating agent aqueous solution condenses with the glass in the drying stage, and the glass and the silane coupling agent are combined.
ガラス処理剤水溶液は、一般的に、シランカップリング剤、界面活性剤、及びｐＨ調整剤を水に混合した水溶液である。ガラス処理剤水溶液中の界面活性剤は、シランカップリング剤を水中に分散・安定化させる作用を有するが、水に対する溶解性が特に低いシランカップリング剤を用いた場合は、シランカップリング剤の水溶液中での分散・安定化の程度が悪化し、調整したガラス処理剤水溶液を長時間に渡って安定的に使用することが困難となる。これまで、種々の界面活性剤を組み合わせる等（例えば、特許文献１等）の試みが行われているが、ガラス処理剤水溶液の安定性が十分であるとは言い難い。
シランカップリング剤をガラス処理剤水溶液中に分散・安定化させる方法として、該ガラス処理剤水溶液中の界面活性剤のシランカップリング剤に対する濃度を増量することも考えられる。しかしながら、界面活性剤はガラスクロスに塗布乾燥された後は不必要となるものであるので、プリント配線板への悪影響を避けるために必要最低量の使用であることが好ましい。
The glass treating agent aqueous solution is generally an aqueous solution in which a silane coupling agent, a surfactant, and a pH adjuster are mixed with water. The surfactant in the glass treating agent aqueous solution has an action of dispersing and stabilizing the silane coupling agent in water, but when a silane coupling agent having particularly low solubility in water is used, The degree of dispersion / stabilization in the aqueous solution deteriorates, and it becomes difficult to stably use the adjusted glass treating agent aqueous solution for a long time. Until now, attempts have been made to combine various surfactants (for example, Patent Document 1), but it is difficult to say that the stability of the glass treating agent aqueous solution is sufficient.
As a method for dispersing and stabilizing the silane coupling agent in the glass treating agent aqueous solution, increasing the concentration of the surfactant in the glass treating agent aqueous solution with respect to the silane coupling agent may be considered. However, since the surfactant is unnecessary after being applied and dried on the glass cloth, it is preferable to use the minimum amount necessary to avoid adverse effects on the printed wiring board.
本発明は、ガラス処理剤水溶液の安定性を界面活性剤の使用量を増加させることなく改善して調整後より長時間に渡って使用可能なガラス処理剤水溶液を得ると共に、ガラスクロス表面に均一にシランカップリング剤が表面処理され、高い耐熱性や機械的強度を発現するガラスクロスとマトリックス樹脂との界面を形成できるガラスクロスの表面処理方法、及び該表面処理を行ったガラスクロスを提供することを目的とする。 The present invention improves the stability of an aqueous glass treating agent solution without increasing the amount of surfactant used, and obtains an aqueous glass treating agent solution that can be used for a longer time after adjustment, and is uniform on the surface of the glass cloth. A glass cloth surface treatment method capable of forming an interface between a glass cloth and a matrix resin, which is surface-treated with a silane coupling agent and exhibits high heat resistance and mechanical strength, and a glass cloth subjected to the surface treatment are provided. For the purpose.
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、ＨＬＢ値が１２．１以上１５．０以下の界面活性剤に対し、ＨＬＢ値が８．６以上１１．０以下の界面活性剤を少量添加することによって、両界面活性剤合計の使用量を増加することなくガラス処理剤水溶液の安定性を改善し、該ガラス処理剤水溶液をガラスクロスに塗布乾燥させることによって、高い耐熱性や機械的強度を発現するガラスクロスとマトリックス樹脂との界面を形成できる効果があることを見出し、この知見に基づいて本発明をなすに至った。
すなわち、本発明のプリント配線基板用のガラスクロス処理剤水溶液は、シランカップリング剤と、界面活性剤とを必須成分とするプリント配線基板用のガラスクロス処理剤水溶液であって、界面活性剤が、ＨＬＢ値が８．６以上１１．０以下の低ＨＬＢ界面活性剤とＨＬＢ値が１２．１以上１５．０以下の高ＨＬＢ界面活性剤とを含み、該低ＨＬＢ界面活性剤の該高ＨＬＢ界面活性剤に対するモル％濃度の比が１／１０００〜１の範囲であり、該界面活性剤の質量％濃度が０．０１〜０．１０の範囲であり、かつシランカップリング剤の質量％濃度の１／５０〜１／５であることを特徴とするプリント配線基板用のガラスクロス処理剤水溶液である。
また、本発明のガラスクロスの表面処理方法は、上記のプリント配線基板用のガラスクロス処理剤水溶液をガラスクロスに塗布して乾燥させることを特徴とするガラスクロスの表面処理方法である。さらに、本発明のガラスクロスは、上記の表面処理方法により処理されたことを特徴とするガラスクロスである。
As a result of intensive studies to solve the above problems, the inventors of the present invention have an HLB value of 8.6 to 11.0 with respect to a surfactant having an HLB value of 12.1 to 15.0. By adding a small amount of surfactant, the stability of the glass treating agent aqueous solution is improved without increasing the total amount of both surfactants used, and the glass treating agent aqueous solution is coated and dried on a glass cloth. It has been found that there is an effect that an interface between a glass cloth and a matrix resin that expresses heat resistance and mechanical strength can be formed, and the present invention has been made based on this finding.
That is, a glass cloth treating agent aqueous solution for a printed wiring board of the present invention, a silane coupling agent, a glass cloth treating agent aqueous solution for a printed wiring board and a surfactant as essential components, surfactant A low HLB surfactant having an HLB value of 8.6 to 11.0 and a high HLB surfactant having an HLB value of 12.1 to 15.0, the high HLB of the low HLB surfactant The ratio of the mol% concentration to the surfactant is in the range of 1/1000 to 1, the mass% concentration of the surfactant is in the range of 0.01 to 0.10, and the mass% concentration of the silane coupling agent. The glass cloth treating agent aqueous solution for printed wiring boards , characterized by being 1/50 to 1/5 of the above.
Moreover, the glass cloth surface treatment method of the present invention is a glass cloth surface treatment method characterized in that the glass cloth treating agent aqueous solution for a printed wiring board is applied to a glass cloth and dried. Furthermore, the glass cloth of the present invention is a glass cloth processed by the surface treatment method described above.
本発明のガラス処理剤水溶液は、界面活性剤の使用量を増加することなくシランカップリング剤の凝集を抑制できることから、調整後の該水溶液を長時間にわたって使用できるという効果を有する。また、本発明のガラスクロスの表面処理方法は、シランカップリング剤の凝集を抑制することでガラスクロス表面に均一にシランカップリング剤が表面処理されるという効果を有する。さらに、本発明のガラスクロスは、高い耐熱性や機械的強度を発現するガラスクロスとマトリックス樹脂との界面を形成できるという効果を有する。 Since the glass treatment agent aqueous solution of the present invention can suppress aggregation of the silane coupling agent without increasing the amount of the surfactant used, it has the effect that the adjusted aqueous solution can be used for a long time. In addition, the glass cloth surface treatment method of the present invention has an effect that the silane coupling agent is uniformly surface-treated on the glass cloth surface by suppressing aggregation of the silane coupling agent. Furthermore, the glass cloth of this invention has the effect that the interface of the glass cloth and matrix resin which expresses high heat resistance and mechanical strength can be formed.
本発明について、以下具体的に説明する。
（Ａ）界面活性剤種
本発明のガラス処理剤水溶液に用いる界面活性剤は、ＨＬＢ値が１２．１以上１５．０以下の界面活性剤（以下、「高ＨＬＢ界面活性剤」という。）とＨＬＢ値が８．６以上１１．０以下の界面活性剤（以下、「低ＨＬＢ界面活性剤」という。）との少なくとも２種を含む混合物（以下、「混合界面活性剤」という。）である。本発明でいうＨＬＢ値とは、界面活性剤の分野で周知のグリフィンの式で定義される値であり、界面活性剤が有する親水基部分の分子量を該界面活性剤の分子量で割り２０をかけることで計算することができる。ＨＬＢ値は、小数点２ケタ以降を四捨五入し、小数点１ケタで表すものとする。
なお、界面活性剤が単体の化合物ではなくＨＬＢ値の分布を有する同種化合物の混合物（例えば、エチレンの付加数が異なるポリオキシエチレンオクチルエーテル）について単にＨＬＢ値という場合は、各成分の重量比に応じた平均ＨＬＢ値を意味するものとし、特に一成分のみのＨＬＢ値は、成分ＨＬＢ値ということとする。たとえば、成分ＨＬＢ値１２．０の化合物１ｇと成分ＨＬＢ値１３．０の化合物２ｇと成分ＨＬＢ値１４．０の化合物１ｇからなる界面活性剤のＨＬＢ値は、（１２．０×１＋１３．０×２＋１４．０×１）／（１＋２＋１）＝１３．０と計算される。
The present invention will be specifically described below.
(A) Surfactant Type The surfactant used in the glass treating agent aqueous solution of the present invention is a surfactant having an HLB value of 12.1 or more and 15.0 or less (hereinafter referred to as “high HLB surfactant”). It is a mixture (hereinafter referred to as “mixed surfactant”) containing at least two kinds of surfactants having an HLB value of 8.6 or more and 11.0 or less (hereinafter referred to as “low HLB surfactant”). . The HLB value as used in the present invention is a value defined by the well-known Griffin formula in the surfactant field, and the molecular weight of the hydrophilic group part possessed by the surfactant is divided by the molecular weight of the surfactant and multiplied by 20. Can be calculated. The HLB value shall be rounded off to the first decimal place and rounded to the first decimal place.
In addition, when the surfactant is not a single compound but a mixture of similar compounds having a distribution of HLB values (for example, polyoxyethylene octyl ethers having different numbers of added ethylene), the HLB value is referred to as the weight ratio of each component. The average HLB value corresponding thereto is meant, and in particular, an HLB value of only one component is referred to as a component HLB value. For example, the HLB value of a surfactant composed of 1 g of a compound having a component HLB value of 12.0, 2 g of a compound having a component HLB value of 13.0, and 1 g of a compound having a component HLB value of 14.0 is (12.0 × 1 + 13.0 × 2 + 14.0 × 1) / (1 + 2 + 1) = 13.0.
また、本発明でいう混合界面活性剤とは、上記に定義した高ＨＬＢ界面活性剤と低ＨＬＢ界面活性剤との少なくとも２種を含む混合物に加えて、成分ＨＬＢ値を横軸（・・・、８．６〜９．０、９．１〜９．５、・・・１４．６〜１５．０、・・・）にとり、該成分ＨＬＢ値を有する成分の合計質量を縦軸にとったヒストグラムを作成したときに、成分ＨＬＢ値が１２．１以上１５．０以下の範囲と８．６以上１１．０以下の範囲のそれぞれに少なくとも１つずつの合計質量のピークを有する界面活性剤（以下、みなし混合界面活性剤という。）を含むものとする。みなし混合界面活性剤の場合は、該ピークを分離することによって高ＨＬＢ界面活性剤と低ＨＬＢ界面活性剤との混合物とみなすものとする。 Further, the mixed surfactant referred to in the present invention refers to the component HLB value on the horizontal axis (...) in addition to the mixture containing at least two types of the high HLB surfactant and the low HLB surfactant defined above. 8.6 to 9.0, 9.1 to 9.5, ... 14.6 to 15.0, ...), and the total mass of the components having the component HLB value is taken on the vertical axis. Surfactant having at least one total mass peak in each of the component HLB values in the range of 12.1 to 15.0 and the range of 8.6 to 11.0 when the histogram is created ( Hereinafter referred to as deemed mixed surfactant). In the case of a deemed mixed surfactant, the peak is separated and regarded as a mixture of a high HLB surfactant and a low HLB surfactant.
高ＨＬＢ界面活性剤のＨＬＢ値は、１２．１以上１５．０以下が好ましく、１３．１以上１４．０以下がより好ましい。ＨＬＢ値が１５．０を超えると、水への親和性が強くなり界面活性剤単独でミセルを形成してしまうことでシランカップリング剤の乳化に対する寄与が減少する。また、ＨＬＢ値が１２．０以下であると、低ＨＬＢ界面活性剤のＨＬＢ値に近づいてしまい、本発明の効果が得られなくなる。
また、低ＨＬＢ界面活性剤のＨＬＢ値は、８．６以上１１．０以下が好ましく、９．１以上１０．０以下がより好ましい。ＨＬＢ値が１１．０を超えると、高ＨＬＢ界面活性剤のＨＬＢ値に近づいてしまい本発明の効果が得られなくなる。また、ＨＬＢ値が８．５以下であると、水への親和性が弱くなることで、シランカップリング剤の水への乳化作用が低下する。
The HLB value of the high HLB surfactant is preferably 12.1 or more and 15.0 or less, and more preferably 13.1 or more and 14.0 or less. When the HLB value exceeds 15.0, the affinity for water increases and the surfactant alone forms micelles, thereby reducing the contribution of the silane coupling agent to emulsification. On the other hand, if the HLB value is 12.0 or less, the HLB value of the low HLB surfactant is approached, and the effects of the present invention cannot be obtained.
In addition, the HLB value of the low HLB surfactant is preferably 8.6 or more and 11.0 or less, and more preferably 9.1 or more and 10.0 or less. When the HLB value exceeds 11.0, the HLB value of the high HLB surfactant is approached and the effect of the present invention cannot be obtained. Moreover, the emulsification effect | action to the water of a silane coupling agent falls because the affinity to water becomes weak that an HLB value is 8.5 or less.
本発明の界面活性剤としては、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤のどの分類の界面活性剤も使用できるが、イオン性の界面活性剤は作業性、特性面から不都合を生じる可能性があるものもあり、非イオン性の界面活性剤を使用することが好ましい。具体的な非イオン性の界面活性剤としては、ポリオキシエチレンオクチルエーテル、ポリオキシエチレンセカンドアルキルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンフェニルエーテルなどを挙げることができる。なお、高ＨＬＢ界面活性剤と低ＨＬＢ界面活性剤との組み合わせは、別種の化合物であっても同種の化合物であっても良いが、非イオン性の界面活性剤同士の組合せであることが好ましく、同種の化合物であることがより好ましい。
高ＨＬＢ界面活性剤と低ＨＬＢ界面活性剤を併用するとガラス処理剤水溶液の安定性が向上する理由は、シランカップリング剤と水との間の界面において、シランカップリング剤−低ＨＬＢ界面活性剤−高ＨＬＢ界面活性剤−水の順で親水性が段階的に変化し、界面活性剤のシランカップリング剤に対する親和性と水に対する親和性を両立させたミセルを効率的に形成することができるためと考えられる。
As the surfactant of the present invention, any type of surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, but ionic surfactants can be used. May cause inconveniences in terms of workability and characteristics, and it is preferable to use a nonionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene second alkyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene phenyl ether. it can. The combination of the high HLB surfactant and the low HLB surfactant may be a different type of compound or the same type of compound, but is preferably a combination of nonionic surfactants. More preferably, they are the same kind of compounds.
The reason why the stability of the glass treating agent aqueous solution is improved when a high HLB surfactant and a low HLB surfactant are used in combination is that the silane coupling agent-low HLB surfactant at the interface between the silane coupling agent and water. -High HLB surfactant-The hydrophilicity changes stepwise in the order of water, and micelles that have both the affinity of the surfactant for the silane coupling agent and the affinity for water can be efficiently formed. This is probably because of this.
（Ｂ）界面活性剤量
混合界面活性剤における２種の界面活性剤の割合は、高ＨＬＢ界面活性剤の量に対し、低ＨＬＢ界面活性剤の量が、モル比で、１／１０００以上、１以下が好ましく、１／２００以上、１以下がより好ましい。低ＨＬＢ界面活性剤の量がモル比で１倍より多いと、水への親和性が低下し、シランカップリング剤の水への乳化作用が低下する。また、低ＨＬＢ界面活性剤の量が１／１０００より少ないと、シランカップリング剤への親和性が低下し、シランカップリング剤の水への乳化作用が低下する。
また、本発明のガラス処理剤水溶液における界面活性剤の合計質量％濃度は、０．０１〜０．１の範囲であることが好ましい。また、該合計質量％濃度は、シランカップリング剤の質量％濃度の１／５０以上、１／５以下が好ましく、１／３０以上、１／８以下がより好ましい。界面活性剤の濃度が１／５を超えると、表面処理後のシランカップリング剤の効果を阻害することがあり、界面活性剤の量が１／５０未満であると、シランカップリング剤の水への乳化作用が低下することがある。
(B) Surfactant amount The ratio of the two surfactants in the mixed surfactant is such that the amount of the low HLB surfactant is 1/1000 or more in terms of molar ratio with respect to the amount of the high HLB surfactant. 1 or less is preferable, 1/20 or more and 1 or less are more preferable. When the amount of the low HLB surfactant is more than 1 time in terms of molar ratio, the affinity for water decreases and the emulsifying action of the silane coupling agent on water decreases. On the other hand, when the amount of the low HLB surfactant is less than 1/1000, the affinity for the silane coupling agent is lowered and the emulsifying action of the silane coupling agent in water is lowered.
Moreover, it is preferable that the total mass% concentration of the surfactant in the glass treating agent aqueous solution of the present invention is in the range of 0.01 to 0.1. The total mass% concentration is preferably 1/50 or more and 1/5 or less, more preferably 1/30 or more and 1/8 or less of the mass% concentration of the silane coupling agent. When the concentration of the surfactant exceeds 1/5, the effect of the silane coupling agent after the surface treatment may be inhibited, and when the amount of the surfactant is less than 1/50, the water of the silane coupling agent The emulsifying action may be reduced.
（Ｃ）シランカップリング剤種
本発明のガラス処理剤水溶液に使用できるシランカップリング剤としては、使用するマトリックス樹脂に対する反応性を有するものであればよい。
例えば、マトリックス樹脂がエポキシ樹脂、ウレタン樹脂、熱硬化性ポリイミド樹脂、メラミン樹脂、エポキシアクリレートや不飽和ポリエステルを硬化させる樹脂、又はこれらのいずれかの組み合わせである場合には、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、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−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及びその塩酸塩、Ｎ−β−（Ｎ−ベンジルアミノエチルアミノプロピル）メチルジメトキシシラン及びその塩酸塩、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルジメトキシシラン等のシラン化合物が好ましい。
なお、本発明における表面処理に使用できるシランカップリング剤は、上記シランカップリング剤の中から好ましいものを１種類、もしくは、複数種類併用して使用することができる。
(C) Silane coupling agent type As the silane coupling agent that can be used in the glass treating agent aqueous solution of the present invention, any silane coupling agent may be used as long as it has reactivity with the matrix resin to be used.
For example, when the matrix resin is an epoxy resin, a urethane resin, a thermosetting polyimide resin, a melamine resin, a resin that cures epoxy acrylate or unsaturated polyester, or any combination thereof, γ- (2-amino Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyl Dimethoxysila And its hydrochloride, N-β- (N-benzylaminoethylaminopropyl) trimethoxysilane and its hydrochloride, N-β- (N-benzylaminoethylaminopropyl) methyldimethoxysilane and its hydrochloride, γ- Silane compounds such as glycidoxypropyltrimethoxysilane and γ-glycidoxypropyldimethoxysilane are preferred.
In addition, the silane coupling agent which can be used for the surface treatment in this invention can use a preferable thing from the said silane coupling agent, or can use it in combination of multiple types.
（Ｄ）シランカップリング剤濃度
本発明のガラス処理剤水溶液中のシランカップリング剤濃度は、０．０５〜５．０質量％であることが好ましく、０．１〜２．０質量％であることがより好ましく、０．２〜１．０質量％であることが最も好ましい。シランカップリング剤濃度が５．０質量％を超える場合はシランカップリング剤の水への乳化状態が不安定になりやすく、０．０５質量％未満の場合はシランカップリング剤の効果が不十分になることがある。
（Ｅ）ガラス処理剤水溶液
本発明のガラス処理剤水溶液は、シランカップリング剤、混合界面活性剤を必須成分とする水溶液であり、溶媒としては水、または、水と水溶性の有機溶媒との混合溶媒が用いられる。又、該ガラス処理剤水溶液には必要に応じて、酢酸等のｐＨ調整剤、染料、顔料、帯電防止剤、潤滑剤などを添加しても良い。
(D) Silane coupling agent concentration The silane coupling agent concentration in the aqueous glass treating agent solution of the present invention is preferably 0.05 to 5.0% by mass, and preferably 0.1 to 2.0% by mass. More preferably, it is most preferable that it is 0.2-1.0 mass%. When the silane coupling agent concentration exceeds 5.0% by mass, the emulsified state of the silane coupling agent in water tends to be unstable, and when it is less than 0.05% by mass, the effect of the silane coupling agent is insufficient. May be.
(E) Glass treating agent aqueous solution The glass treating agent aqueous solution of the present invention is an aqueous solution containing a silane coupling agent and a mixed surfactant as essential components, and the solvent is water or water and a water-soluble organic solvent. A mixed solvent is used. Moreover, you may add pH adjusters, such as an acetic acid, dye, a pigment, an antistatic agent, a lubricant, etc. to this glass treating agent aqueous solution as needed.
（Ｆ）ガラスクロスへの表面処理剤の付着量
ガラスクロスに対するシランカップリング剤と混合界面活性剤の付着量の和は０．０３〜０．３質量％が好ましい。この付着量とは強熱減量により測定した有機成分の重量減分を意味するものとする。付着量が０．３質量％より多いと、ガラスクロスへのマトリックス樹脂の含浸が阻害されることがあり、付着量が０．０３質量％より少ないと、シランカップリング剤の効果が低下する。
（Ｇ）表面処理方法
本発明のガラスクロスの表面処理方法は、浸漬法、噴霧法、ガス化法等の任意の公知の方法で上述したガラス処理剤水溶液を塗布する方法を採用できる。その後の該水溶液を乾燥する方法としては、熱風、電磁波、等公知の方法が使用できる。なお、本発明の表面処理方法を適用するガラスクロスは、プリント配線板用として好適に使用されるガラスクロスであるので、Ｅガラスからなるガラスクロスが特に好ましく使用できる。
（Ｈ）プリント配線板用積層板の製造
本発明の表面処理方法によって表面処理したガラスクロスを用いてプリント配線板用積層板を製造するには常法に従えばよく、例えば該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溶媒に溶解させたワニスを含浸させて乾燥した樹脂含浸プリプレグを作り、これを複数枚積層し、または内層コア板の上にこれを複数枚または１枚積層し、加熱加圧成形することにより得られる。
(F) Adhesion amount of surface treatment agent to glass cloth The sum of the adhesion amount of the silane coupling agent and the mixed surfactant to the glass cloth is preferably 0.03 to 0.3 mass%. This amount of adhesion shall mean the weight loss of the organic component measured by loss on ignition. When the adhesion amount is more than 0.3% by mass, the impregnation of the matrix resin into the glass cloth may be inhibited. When the adhesion amount is less than 0.03% by mass, the effect of the silane coupling agent is lowered.
(G) Surface treatment method As the surface treatment method of the glass cloth of the present invention, a method of applying the glass treating agent aqueous solution described above by any known method such as a dipping method, a spray method, a gasification method, or the like can be adopted. As a method for drying the aqueous solution thereafter, known methods such as hot air and electromagnetic waves can be used. In addition, since the glass cloth which applies the surface treatment method of this invention is a glass cloth used suitably for printed wiring boards, the glass cloth which consists of E glass can use especially preferably.
(H) Manufacture of laminated board for printed wiring board In order to produce a laminated board for printed wiring board using the glass cloth surface-treated by the surface treatment method of the present invention, for example, epoxy may be applied to the glass cloth. A resin-impregnated prepreg made by impregnating a varnish obtained by dissolving a matrix resin such as a resin in a solvent is dried, and a plurality of these are laminated, or a plurality or one is laminated on the inner core plate and heated. It can be obtained by pressure molding.
本発明を実施例に基づいてより詳しく説明する。下記の３項目を、各実施例、比較例で得られたサンプルに対しそれぞれ測定し、結果を表１に示した。
（Ｉ）ガラス処理剤水溶液の安定性
ガラス処理剤水溶液を調整後、それぞれ２４時間、７２時間、１２０時間放置してからガラスクロスを浸漬することによって表面処理を行い、該処理後の該水溶液の白度を吸光度計（日本分光株式会社製；Ｖ−５５０）にて測定した。そして、該水溶液作成直後の白度からの変化の度合いを評価した。
（II）レジンはじきの発生頻度
ガラス処理剤水溶液を調整後、それぞれ２４ｈ、７２ｈ、１２０ｈ放置してからガラスクロスの表面処理を行い、表面処理した該ガラスクロスを使用してプリプレグを作成し、それぞれ、５００ｍｍ角の試験片に切り出したのち、試験片２０枚中において、直径１ｍｍ以上のレジンはじきが発生した試験片の枚数を評価した。
（III）プリント配線板用積層板のはんだ耐熱性
ガラス処理剤水溶液を調整後、それぞれ２４ｈ、７２ｈ、１２０ｈ放置してからガラスクロスの表面処理を行い、表面処理した該ガラスクロスを使用した積層板を作成し、それぞれ、５０ｍｍ角の試験片に切り出したのち、試験片を１２１℃・１気圧加圧のＰＣＴ条件にさらし、２８８℃のはんだ浴に２０秒浸して、試験片４枚中において、直径３ｍｍ以上の膨れが発生した試験片の枚数を評価した。
The present invention will be described in more detail based on examples. The following three items were measured for the samples obtained in each Example and Comparative Example, and the results are shown in Table 1.
(I) Stability of glass treating agent aqueous solution After adjusting the glass treating agent aqueous solution, the glass treating agent aqueous solution was left to stand for 24 hours, 72 hours, and 120 hours, respectively, and surface treatment was performed by immersing the glass cloth. Whiteness was measured with an absorptiometer (manufactured by JASCO Corporation; V-550). Then, the degree of change from whiteness immediately after the aqueous solution was created was evaluated.
(II) Frequency of resin repellency After adjusting the glass treating agent aqueous solution, the glass cloth was surface-treated after being left for 24 h, 72 h, and 120 h, respectively, and a prepreg was prepared using the surface-treated glass cloth, After cutting into 500 mm square test pieces, the number of test pieces in which resin repelling with a diameter of 1 mm or more occurred in 20 test pieces was evaluated.
(III) Solder heat resistance of laminated board for printed wiring board After the glass treating agent aqueous solution is prepared, the glass cloth is surface-treated after being left for 24 h, 72 h, and 120 h, respectively, and the laminated board using the surface-treated glass cloth. After each was cut out into 50 mm square test pieces, the test pieces were exposed to PCT conditions of 121 ° C. and 1 atm pressure, immersed in a solder bath at 288 ° C. for 20 seconds, and in four test pieces, The number of test pieces in which swelling with a diameter of 3 mm or more occurred was evaluated.
［実施例１］
（ａ）ガラスクロス
常法により脱油処理した下記仕様の旭シュエーベル（株）製；２１１６（商品名）を用いた。
＜ガラスクロス仕様＞
糸使い： Ｅ２２５ １／０ × Ｅ２２５ １／０
密度： 経糸６０本／２５ｍｍ × 緯糸５８本／２５ｍｍ
目付： １０４ｇ／ｍ2
厚み： ０．０９５ｍｍ
（ｂ）界面活性剤
高ＨＬＢ界面活性剤としてＨＬＢ値が１３．６であるポリオキシエチレンオクチルフェニルエーテル界面活性剤（三洋化成（株）製；オクタポール１００）を使用し、低ＨＬＢ界面活性剤としてＨＬＢ値が９．６であるポリオキシエチレンオクチルフェニルエーテル界面活性剤（三洋化成（株）製；オクタポール４５）を使用した混合界面活性剤を用い、２種の界面活性剤量の割合が、高ＨＬＢ界面活性剤の量に対し、低ＨＬＢ界面活性剤の量が、モル比で１／１００になるように配合して混合界面活性剤を得た。
[Example 1]
(A) Glass cloth 2116 (trade name) manufactured by Asahi Schwer Co., Ltd. having the following specifications, which was deoiled by a conventional method, was used.
<Glass cloth specification>
Yarn use: E225 1/0 × E225 1/0
Density: 60 warps / 25mm x 58 wefts / 25mm
Weight per unit: 104g / m 2
Thickness: 0.095mm
(B) Surfactant A polyoxyethylene octyl phenyl ether surfactant (manufactured by Sanyo Chemical Co., Ltd .; Octapol 100) having an HLB value of 13.6 is used as a high HLB surfactant, and a low HLB surfactant. As a mixed surfactant using a polyoxyethylene octylphenyl ether surfactant (manufactured by Sanyo Chemical Co., Ltd .; Octapol 45) having an HLB value of 9.6, the ratio of the two surfactant amounts is The mixed surfactant was obtained by blending so that the amount of the low HLB surfactant was 1/100 in terms of molar ratio with respect to the amount of the high HLB surfactant.
（ｃ）ガラス処理剤水溶液
シランカップリング剤として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・塩酸塩（東レ・ダウコーニング・シリコーン（株）製；ＳＺ６０３２）を用い、該シランカップリング剤を固形分として０．５質量％、酢酸を０．０５質量％、（ｂ）で得た混合界面活性剤を０．０５質量％を水に混合して、マグネチックスターラーにて１時間攪拌し、実施例１のガラス処理剤水溶液とした。
（ｄ）ガラスクロスの表面処理
（ａ）のガラスクロスを（ｃ）で得たガラス処理剤水溶液に浸漬し、ピックアップが３０質量％になるように絞液したあと、１７０℃で３０秒加熱乾燥した。得られたガラスクロスを５００ｍｍ×３５０ｍｍにカットし、表面処理ガラスクロス片とした。
(C) Glass treating agent aqueous solution As a silane coupling agent, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Silicone Co., Ltd .; SZ6032) was used. And 0.5% by mass of the silane coupling agent as a solid content, 0.05% by mass of acetic acid, and 0.05% by mass of the mixed surfactant obtained in (b) are mixed with water. The mixture was stirred with a stirrer for 1 hour to obtain an aqueous glass treating agent solution of Example 1.
(D) Surface treatment of glass cloth (a) The glass cloth of (a) is immersed in the glass treating agent aqueous solution obtained in (c), squeezed so that the pickup becomes 30% by mass, and then heated and dried at 170 ° C. for 30 seconds did. The obtained glass cloth was cut into a size of 500 mm × 350 mm to obtain a surface-treated glass cloth piece.
（ｅ）プリプレグの製造
（ｄ）で得た表面処理ガラスクロス片を、下記組成のエポキシ樹脂ワニス（ＦＲ−５処方）に浸漬し、１５０℃で４分間予備乾燥してマトリックス樹脂分５０質量％のプリプレグを得た。
［エポキシ樹脂ワニス組成］
Ｅ１５７Ｓ７０Ｂ７５（油化シェルエポキシ（株）商品名）：２５質量部
Ｅ５０５０Ｔ６０（油化シェルエポキシ（株）商品名）：２５質量部
８３４Ｂ７５（油化シェルエポキシ（株）商品名）：５質量部
ＹＬＨ１２９Ｂ６５（油化シェルエポキシ（株）商品名）：２５質量部
２−エチル−４−メチルイミダゾール：１質量部
２−メトキシエタノール：２０質量部
（ｆ）積層板の製造
（ｅ）で得たプリプレグを４枚積層し、さらにその上に１２μの銅箔を重ねて常法により１９５℃、４０ｋｇｆ／ｃｍ2 で一時間加熱加圧して板厚が０．４ｍｍの積層板を得た。
(E) Manufacture of prepreg The surface-treated glass cloth piece obtained in (d) was immersed in an epoxy resin varnish (FR-5 formulation) having the following composition, pre-dried at 150 ° C. for 4 minutes, and a matrix resin content of 50% by mass. Prepreg was obtained.
[Epoxy resin varnish composition]
E157S70B75 (trade name of Yuka Shell Epoxy Co., Ltd.): 25 parts by mass E5050T60 (trade name of Yuka Shell Epoxy Co., Ltd.): 25 parts by mass 834B75 (trade name of Yuka Shell Epoxy Co., Ltd.): 5 parts by weight YLH129B65 ( (Oilized Shell Epoxy Co., Ltd., trade name): 25 parts by mass 2-ethyl-4-methylimidazole: 1 part by mass 2-methoxyethanol: 20 parts by mass (f) Production of laminate 4 Then, 12 μm copper foil was laminated thereon, and heated and pressed at 195 ° C. and 40 kgf / cm 2 for 1 hour by a conventional method to obtain a laminated plate having a thickness of 0.4 mm.
［実施例２］
実施例１（ｂ）において、オクタポール１００のかわりに、ＨＬＢ値が１３．３であるポリオキシエチレン高級アルコール界面活性剤（三洋化成（株）製；ナロアクティＨＮ１００）を用いた以外は、実施例１と同様の方法で、実施例２のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
［実施例３］
実施例１（ｂ）において、２種の界面活性剤量の割合が、高ＨＬＢ界面活性剤の量に対し、低ＨＬＢ界面活性剤の量が、モル比で１になるように配合した以外は、実施例１と同様の方法で実施例３のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
[Example 2]
In Example 1 (b), instead of Octapol 100, a polyoxyethylene higher alcohol surfactant (manufactured by Sanyo Chemical Co., Ltd .; NAROACTY HN100) having an HLB value of 13.3 was used. 1 was used to obtain the glass treating agent aqueous solution, the prepreg, and the laminate of Example 2.
[Example 3]
In Example 1 (b), except that the proportion of the two surfactant amounts was such that the amount of the low HLB surfactant was 1 in molar ratio to the amount of the high HLB surfactant. In the same manner as in Example 1, the glass treating agent aqueous solution, prepreg, and laminate were obtained in Example 3.
［実施例４］
実施例１（ｃ）において、（ｂ）で得た混合界面活性剤を０．０１質量％にした以外は、実施例１と同様の方法で実施例４のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
［実施例５］
実施例１（ｃ）において、（ｂ）で得た混合界面活性剤を０．１０質量％にした以外は、実施例１と同様の方法で実施例５のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
[Example 4]
In Example 1 (c), the glass treating agent aqueous solution, prepreg, and laminate of Example 4 were prepared in the same manner as in Example 1 except that the mixed surfactant obtained in (b) was 0.01% by mass. I got a plate.
[Example 5]
In Example 1 (c), the glass treating agent aqueous solution, prepreg, and laminate of Example 5 were prepared in the same manner as in Example 1 except that the mixed surfactant obtained in (b) was changed to 0.10% by mass. I got a plate.
［実施例６］
実施例１（ｂ）において、２種の界面活性剤量の割合が、高ＨＬＢ界面活性剤の量に対し、低ＨＬＢ界面活性剤の量が、モル比で１／１０００になるように配合した以外は、実施例１と同様の方法で実施例６のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
［実施例７］
実施例１（ｂ）において、オクタポール４５のかわりに、ＨＬＢ値が８．６であるソルビタンモノラウレート界面活性剤（花王（株）製；レオドールＳＰ−Ｌ１０）を用いた以外は、実施例１と同様の方法で、実施例７のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
[Example 6]
In Example 1 (b), the proportion of the two surfactants was blended so that the amount of the low HLB surfactant was 1/1000 in terms of the molar ratio with respect to the amount of the high HLB surfactant. Except for the above, the glass treating agent aqueous solution, prepreg, and laminated plate of Example 6 were obtained in the same manner as in Example 1.
[Example 7]
In Example 1 (b), except that sorbitan monolaurate surfactant (manufactured by Kao Corp .; Rheodor SP-L10) having an HLB value of 8.6 was used instead of Octapol 45. 1 was used to obtain an aqueous glass treating agent solution, a prepreg, and a laminated plate of Example 7.
［比較例１］
実施例１（ｂ）において、オクタポール１００のみを用いた以外は、実施例１と同様の方法で、比較例１のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
［比較例２］
実施例１（ｂ）において、オクタポール１００のかわりに、ＨＬＢ値が１７．９であるポリオキシエチレンオクチルフェニルエーテル界面活性剤（三洋化成（株）製；オクタポール４００）を用いた以外は、実施例１と同様の方法で、比較例２のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
[Comparative Example 1]
In Example 1 (b), a glass treating agent aqueous solution, a prepreg, and a laminate were obtained in the same manner as in Example 1 except that only Octapol 100 was used.
[Comparative Example 2]
In Example 1 (b), a polyoxyethylene octylphenyl ether surfactant having a HLB value of 17.9 (manufactured by Sanyo Chemical Co., Ltd .; Octapol 400) was used in place of Octapole 100. In the same manner as in Example 1, a glass treating agent aqueous solution, a prepreg, and a laminate were obtained in Comparative Example 2.
［比較例３］
実施例１（ｂ）において、２種の界面活性剤量の割合が、高ＨＬＢ界面活性剤の量に対し、低ＨＬＢ界面活性剤の量が、モル比で２０になるように配合した以外は、実施例１と同様の方法で、比較例３のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
［比較例４］
実施例１（ｃ）において、混合界面活性剤の濃度を０．００５質量％とした以外は、実施例１と同様の方法で、比較例４のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
[Comparative Example 3]
In Example 1 (b), except that the proportion of the two surfactant amounts was such that the amount of the low HLB surfactant was 20 in terms of molar ratio with respect to the amount of the high HLB surfactant. In the same manner as in Example 1, the glass treating agent aqueous solution, prepreg, and laminate were obtained in Comparative Example 3.
[Comparative Example 4]
In Example 1 (c), the glass treating agent aqueous solution, prepreg, and laminate were obtained in the same manner as in Example 1 except that the concentration of the mixed surfactant was 0.005% by mass. It was.
［比較例５］
実施例１（ｂ）において、オクタポール４５のかわりに、ＨＬＢ値が７．５であるポリオキシエチレンノニルフェニルエーテル界面活性剤（松本油脂（株）製；ＭＹＮ−１０８）を用い、２種の界面活性剤量の割合が、高ＨＬＢ界面活性剤の量に対し、低ＨＬＢ界面活性剤の量が、重量比で２になるように配合し、実施例１（ｃ）において、（ｂ）で得た混合界面活性剤を０．１０質量％にした以外は、実施例１と同様の方法で、比較例５のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
［比較例６］
比較例５において、ＭＹＮ−１０８のかわりに、ＨＬＢ値が８．０であるポリオキシエチレン高級アルコール界面活性剤（ライオン（株）製；レオコールＴＤ−３０）を用いた以外は、比較例５と同様の方法で、比較例６のガラス処理剤水溶液、プリプレグ、及び積層板を得た。
[Comparative Example 5]
In Example 1 (b), a polyoxyethylene nonylphenyl ether surfactant having an HLB value of 7.5 (manufactured by Matsumoto Yushi Co., Ltd .; MYN-108) was used in place of Octapol 45. In Example 1 (c), the ratio of the amount of the surfactant was such that the amount of the low HLB surfactant was 2 by weight with respect to the amount of the high HLB surfactant. A glass treating agent aqueous solution, prepreg, and laminate were obtained in the same manner as in Example 1 except that the obtained mixed surfactant was changed to 0.10% by mass.
[Comparative Example 6]
In Comparative Example 5, in place of MYN-108, a polyoxyethylene higher alcohol surfactant having a HLB value of 8.0 (manufactured by Lion Corporation; Leocol TD-30) was used. By the same method, the glass treating agent aqueous solution, prepreg, and laminated board of the comparative example 6 were obtained.
本発明のガラス処理剤水溶液、該水溶液を使用したガラスクロスの表面処理方法、及び該表面処理を行ったガラスクロスは、プリント基板用途のガラスクロスの分野で好適に利用できる。 The glass treating agent aqueous solution of the present invention, the glass cloth surface treatment method using the aqueous solution, and the glass cloth subjected to the surface treatment can be suitably used in the field of glass cloth for printed circuit boards.
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| WO2022215288A1 (en) * | 2021-04-09 | 2022-10-13 | 旭化成株式会社 | Glass cloth, prepreg, and printed wiring board |
| KR20230129502A (en) * | 2021-04-09 | 2023-09-08 | 아사히 가세이 가부시키가이샤 | Glass cloth, prepreg and printed wiring board |
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