JPS63175138A - Production of glass cloth for laminate plate - Google Patents
Production of glass cloth for laminate plateInfo
- Publication number
- JPS63175138A JPS63175138A JP62001113A JP111387A JPS63175138A JP S63175138 A JPS63175138 A JP S63175138A JP 62001113 A JP62001113 A JP 62001113A JP 111387 A JP111387 A JP 111387A JP S63175138 A JPS63175138 A JP S63175138A
- Authority
- JP
- Japan
- Prior art keywords
- glass cloth
- glass
- warp
- threads
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims description 36
- 239000004744 fabric Substances 0.000 title description 24
- 238000004519 manufacturing process Methods 0.000 title description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920000554 ionomer Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 description 14
- 238000004513 sizing Methods 0.000 description 13
- 238000009990 desizing Methods 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 6
- 238000009941 weaving Methods 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 aliphatic isocyanate Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Landscapes
- Reinforced Plastic Materials (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Woven Fabrics (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は製繊性が良く、得られたガラスクロスの表面毛
羽が少なく、電気絶縁用積層板特性、特にはんだ耐熱性
に優れた積層板用ガラスクロスの製造法に関するもので
ある。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a laminate that has good fibre-making properties, has little surface fuzz on the obtained glass cloth, and has excellent electrical insulation laminate properties, especially solder heat resistance. The present invention relates to a method for manufacturing glass cloth for use.
（従来の技術）
積層板用ガラスクロスを製造するには、以下の方法が一
般に行なわれている。即ちクレー等のガラス原料を溶融
・紡糸しモノフィラメントをつくり、紡糸のしやすさ、
加熱・整経・製織等の後工程での加工性を満足させる目
的でスターチを主成分とするサイジング剤で一次サイジ
ングをし必要本数集束しガラスストランドとし、加熱し
てスターチ系サイズトガラス糸とし、この糸をＩＩして
ガラスクロスとし、−次サイジング剤を加熱除去（脱サ
イジング）シ、その後の用途に応じた処理でおるカップ
リング剤等の二次表面処理をして製造している。(Prior Art) The following method is generally used to manufacture glass cloth for laminated plates. In other words, by melting and spinning glass raw materials such as clay to create monofilaments, the ease of spinning,
In order to satisfy processability in post-processes such as heating, warping, and weaving, we perform primary sizing with a sizing agent mainly composed of starch, bundle the required number of strands to form glass strands, and heat them to form starch-based sized glass threads. This thread is made into a glass cloth, the sizing agent is removed by heating (desizing), and the cloth is then subjected to a secondary surface treatment with a coupling agent or the like according to the intended use.
この方法は脱サイジング工程を必要とするため。This method requires a desizing step.
加熱除去等の脱サイジング工程でガラス糸が著しく劣化
し、ガラスクロスの抗張力が脱サイジング工程前のそれ
よりも大巾に低下するために、ガラスクロスとしての補
強効果が低下すること、およびエネルギー消費量の大き
い脱サイジング及び二次処理工程を経るため、コスト高
なものになるという問題点を有してＪ３す、これらの問
題点を解決するために９本発明者等は、以前上述の脱す
イジングエ稈や二次表面処理工程を省略できる。即ら織
上げたクロスがそのまま樹脂と共に成形できる（＝以下
ダイレクトクロス法と呼７玉）ガラス繊維サイジング剤
（プラスチック系ザイズドガラス糸）を提案した（特開
昭５７−８２１４８号）が、このガラスクロスは樹脂の
Ｓ浸性は良好で、得られた積層板の強度は高い。The glass thread deteriorates significantly during the desizing process such as heat removal, and the tensile strength of the glass cloth decreases significantly compared to that before the desizing process, which reduces the reinforcing effect of the glass cloth and reduces energy consumption. J3 has the problem of high cost due to the large amount of desizing and secondary treatment steps.In order to solve these problems, the present inventors previously proposed Ising culm and secondary surface treatment steps can be omitted. In other words, we proposed a glass fiber sizing agent (plastic-based sized glass thread) that allows the woven cloth to be molded as is with resin (hereinafter referred to as the direct cloth method) (Japanese Patent Application Laid-open No. 57-82148), but this glass cloth The resin has good S-immersion properties, and the strength of the obtained laminate is high.
しかしながら経糸に糊付をしていないためガラスクロス
の製織中に経糸のフィラメント切れが起こり易く、ガラ
スクロスの表面毛羽が多いという問題点を残していた。However, since the warp threads are not glued, filaments of the warp threads are likely to break during weaving of the glass cloth, and the problem remains that the surface of the glass cloth has a lot of fuzz.
一方、前述のスターチを成分と覆る従来法のサイジング
剤で一次サイジング後加熱しガラス糸としガラスクロス
に織る場合には、経糸の毛羽立ちを防ぐためにポリビニ
ルアルコールやスターチ等で糊付（二次サイジング）を
施しているが、ポリビニルアルコールやスターチはエポ
キシ樹脂等との親和性が悪いため１本発明でいうダイレ
クトクロス法には適用できない。本発明者等は１以上の
本問題を解決するため製織加工上必要な経糸糊剤につい
て鋭意検問した結果。On the other hand, in the case of primary sizing using a conventional sizing agent that covers the starch as an ingredient, heating it to form glass threads and weaving them into glass cloth, sizing with polyvinyl alcohol or starch (secondary sizing) is required to prevent warp threads from fuzzing. However, since polyvinyl alcohol and starch have poor affinity with epoxy resins, etc., they cannot be applied to the direct cross method referred to in the present invention. In order to solve one or more of these problems, the inventors of the present invention have made extensive inquiries regarding the warp sizing agent necessary for weaving processing.
製織加工性が良好で出来たガラスクロスをそのまま樹脂
と共に成形して得られる積層板の電気特性。Electrical properties of a laminate obtained by molding glass cloth with good weaving processability as it is together with resin.
耐熱性等の諸性性に優れるガラスクロスの製造法を見い
出したものである。We have discovered a method for manufacturing glass cloth that has excellent properties such as heat resistance.
（発明の目的）
本発明の目的は、従来のガラスクロスの製造法が有する
前述の問題点を解決し、ガラスクロスの表面毛羽が少な
り、脱サイジング及び二次表面処理を必要とせず、かつ
又製織性が良好で電気絶縁用積層板特性、特にはんだ耐
熱性に優れた積層板用ガラスクロスの製造法を提供する
事にある。(Objective of the Invention) The object of the present invention is to solve the above-mentioned problems of the conventional glass cloth manufacturing method, to reduce the surface fuzz of the glass cloth, and to eliminate the need for desizing and secondary surface treatment. Another object of the present invention is to provide a method for manufacturing a glass cloth for laminated plates that has good weavability and excellent properties for electrically insulating laminated plates, especially solder heat resistance.
（発明の構成）
本発明は、プラスチックサイズ系ガラス糸に以下に述べ
る特殊な糊剤を付着せしめて経糸とし。(Structure of the Invention) In the present invention, a special sizing agent described below is attached to plastic-sized glass threads to form warp threads.
プラスチックサイズ系ガラス糸を緯糸として構成せしめ
ることを特徴とする積層板用ガラスクロスの製造法でお
る。A method for manufacturing a glass cloth for laminated plates, characterized in that plastic-sized glass threads are used as weft threads.
本発明に用いるフィルム形成剤はエポキシ樹脂。The film forming agent used in the present invention is an epoxy resin.
ウレタン樹脂、ポリイミド樹脂、アイオノマー樹脂及び
これらの変性樹脂の内少なくとも１種からなる。It consists of at least one kind of urethane resin, polyimide resin, ionomer resin, and modified resins thereof.
ざらに詳しくはエポキシ樹脂としてはビスフェノールＡ
／エピクロルヒドリン型エポキシ樹脂。For more details, the epoxy resin is bisphenol A.
/Epichlorohydrin type epoxy resin.
ノボラック型エポキシ樹脂、ウレタン変性エポキシ樹脂
等があげられる。Examples include novolac type epoxy resin, urethane-modified epoxy resin, and the like.
ウレタン樹脂は脂肪族系ポリウレタン樹脂であり、脂肪
族系ポリエステル、脂肪族系ポリエーテルと脂肪族系イ
ソシアネートとの反応生成物である。The urethane resin is an aliphatic polyurethane resin, and is a reaction product of an aliphatic polyester, an aliphatic polyether, and an aliphatic isocyanate.
ポリイミド樹脂は仝芳呑族ポリピロメツドアミド、仝芳
香族ポリイミド、ポリエーテルイミド。Polyimide resins include aromatic polypyromethamide, aromatic polyimide, and polyetherimide.
ポリアミドイミド、ポリアミノビスマレイド等があげら
れる。Examples include polyamideimide and polyamino bismaleide.
アイオノマー樹脂は下記に示されるものでおる。The ionomer resins are shown below.
００Ｍ ：Ｎａ 、Ｚｎ２＋ Ｍ＋ ０− ０ 。00M: Na, Zn2+ M+ 0- 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
また、潤滑剤はポリエチレンイミン、変性シリコーンオ
イル及びイミダゾリン系界面活性剤の内少なくとも１種
類からなる。The lubricant is made of at least one of polyethyleneimine, modified silicone oil, and imidazoline surfactant.
ポリエチレンイミンは
で示されるもので重合度ｎ＝１０００以上のものが好ま
しい。The polyethyleneimine is represented by and preferably has a degree of polymerization n=1000 or more.
変性シリコーンオイルはポリエーテル変性シリコーンオ
イル、エポキシ変性シリコーンオイル。Modified silicone oil includes polyether modified silicone oil and epoxy modified silicone oil.
アミン変性シリコーンオイル、カルボキシル変性シリコ
ーンオイル等があげられる。Examples include amine-modified silicone oil and carboxyl-modified silicone oil.
イミダゾリン系界面活性剤は下記に示されるものである
。The imidazoline surfactants are shown below.
Ｒ’ −Ｃ＝へ一〇Ｈ２
１ＩＩ Ｒ’、Ｒ″：アルキル基
Ｎ−ＣＨ２または
１ アルケニル基Ｒ″
配合量はフィルム形成剤１００平量部に対し、潤滑剤１
０〜４０重量部が好ましい。R' -C=he10H2 1II R', R'': Alkyl group N-CH2 or 1 Alkenyl group R'' The amount is 1 lubricant per 100 parts by weight of film forming agent.
0 to 40 parts by weight is preferred.
上記のフィルム形成剤と潤滑剤を配合し、水性の経糸用
糊剤を得る。これをプラスチックサイズ系カラス糸に対
して０．０５〜５重開％塗布乾燥し、経糸とする。この
経糸を使ってプラスチックサイズ系ガラス糸を緯糸とし
て製織しガラスクロ付表２゜
スとし、脱サイジングおよび二次表面処理をすることな
く電気絶縁用積層板の製造に使用する。The above film forming agent and lubricant are blended to obtain an aqueous warp sizing agent. This is applied to plastic size crow threads at a rate of 0.05 to 5 folds and dried to form warp threads. The warp yarns are used to weave plastic-sized glass yarns as weft yarns to form a glass cloth-attached surface of 2°, which is used to manufacture electrically insulating laminates without desizing or secondary surface treatment.
以下に実施例及び比較例で本発明を具体的に説明する。The present invention will be specifically explained below using Examples and Comparative Examples.
（実施例）
付表１および付表２に記載した実施例１〜１０の経糸糊
剤をそれぞれ配合し、太さ６７．５ｔｅＸのプラスデッ
クサイズ系のガラス糸に塗布し。(Example) The warp sizing agents of Examples 1 to 10 listed in Attached Table 1 and Attached Table 2 were each blended and applied to a plus deck size glass thread having a thickness of 67.5 teX.
経糸を得た。この経糸及び前記のプラスチックサイズ系
ガラス糸を緯糸に使用し、経糸密度が４４本／２５％、
緯糸密度が３３本／２５履のガラスクロスを１ｑだ。
これらのガラスクロスを公知の方法でエポキシ樹脂のワ
ニスを塗工してプリプレグを得た。その後プリプレグを
８枚重ねて温度１６８°Ｃ，プレス圧８０に’Ｊ／ｃｒ
ｔｔでプレス成型し、１゜５ｍ厚のエポキシ樹脂積層板
を作製した。I got the warp. This warp and the above-mentioned plastic size glass thread are used for the weft, and the warp density is 44/25%.
1q of glass cloth with a weft density of 33 threads/25 shoes.
These glass cloths were coated with epoxy resin varnish by a known method to obtain prepregs. After that, 8 sheets of prepreg were stacked at a temperature of 168°C and a press pressure of 80'J/cr.
Press molding was performed using tt to produce an epoxy resin laminate with a thickness of 1.5 m.
このエポキシ樹脂積層板から５０ＩｒＩＩ１１角の試片
を切り出して１２１℃の水蒸気オートクレーブ中に１時
間入れて吸湿処理した。この試片を２６０°Ｃのはんだ
浴に３分間浸漬して外観の変化を肉眼で観察した。A 11 square piece of 50IrII was cut out from this epoxy resin laminate and placed in a steam autoclave at 121° C. for 1 hour to absorb moisture. This test piece was immersed in a 260°C solder bath for 3 minutes, and changes in appearance were observed with the naked eye.
（比較例）
付表３中に記載した比較例１〜４の経糸用糊剤を配合し
、実施例と同様の方法で評価した。(Comparative Example) The warp sizing agents of Comparative Examples 1 to 4 listed in Appendix 3 were blended and evaluated in the same manner as in the Examples.
付表１．付表２および付表３の比較から本発明のガラス
クロスのＩｎ法によれば製織時の毛羽発生が極めて少な
り、優れた積層板用ガラスクロスが得られる。また、積
層板のはんだ耐熱性等の特性にも好結果を与えることが
わかる。Appendix 1. From a comparison of Appendix Tables 2 and 3, the In method of producing the glass cloth of the present invention results in very little fluff during weaving, and provides an excellent glass cloth for laminated plates. It can also be seen that good results are obtained in properties such as solder heat resistance of the laminate.
（発明の効果）
本発明の積層板用ガラスクロスの製造法に使用される経
糸用糊剤は潤滑剤を配合しであるため。(Effects of the Invention) The warp glue used in the method of manufacturing the glass cloth for laminated plates of the present invention contains a lubricant.
経糸に平滑性を付与することができ、この経糸は！！！
織性に優れる。This warp can give smoothness to the warp! ! !
Excellent weavability.
また、この経糸用糊剤はエポキシ樹脂積層板の製造に使
用するエポキシ樹脂との親和性に優れるため、ダイレク
トクロス法に於いて積層板の特性特に吸湿後のはんだ耐
熱性に優れている。In addition, this warp glue has excellent affinity with the epoxy resin used in the production of epoxy resin laminates, and therefore, in the direct cross method, the laminates have excellent properties, especially the soldering heat resistance after moisture absorption.
特許出願人 富士ファイバーグラス株式会社第１頁
の絖きPatent applicant: Fuji Fiberglass Co., Ltd. Page 1
Claims (1)
脂、ポリイミド樹脂、アイオノマー樹脂及び、これらの
変性樹脂の内、少なくとも１種からなり潤滑剤（Ｂ）と
してポリエチレンイミン。 変性シリコーンオイル、及びイミダゾリン系界面活性剤
の内少なくとも１種からなり、上記フィルム形成剤（Ａ
）と潤滑剤（Ｂ）の配合物をプラスチックサイズを施し
たガラス糸に付着せしめ経糸とし、プラスチックサイズ
を施したガラス糸を緯糸として構成せしめることを特徴
とする積層板用ガラスクロスの製造法。[Scope of Claims] The film forming agent (A) is composed of an epoxy resin, a urethane resin, a polyimide resin, an ionomer resin, and at least one of these modified resins, and the lubricant (B) is polyethyleneimine. The above film forming agent (A
) and a lubricant (B) are attached to plastic-sized glass threads as warp threads, and the plastic-sized glass threads are used as weft threads.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62001113A JPS63175138A (en) | 1987-01-08 | 1987-01-08 | Production of glass cloth for laminate plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62001113A JPS63175138A (en) | 1987-01-08 | 1987-01-08 | Production of glass cloth for laminate plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63175138A true JPS63175138A (en) | 1988-07-19 |
Family
ID=11492408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62001113A Pending JPS63175138A (en) | 1987-01-08 | 1987-01-08 | Production of glass cloth for laminate plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63175138A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047416A (en) * | 2000-05-25 | 2002-02-12 | Wacker Asahikasei Silicone Co Ltd | Silane compound for treating glass fiber |
-
1987
- 1987-01-08 JP JP62001113A patent/JPS63175138A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047416A (en) * | 2000-05-25 | 2002-02-12 | Wacker Asahikasei Silicone Co Ltd | Silane compound for treating glass fiber |
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