JP2580905B2 - Manufacturing method of prepreg - Google Patents
Manufacturing method of prepregInfo
- Publication number
- JP2580905B2 JP2580905B2 JP3255642A JP25564291A JP2580905B2 JP 2580905 B2 JP2580905 B2 JP 2580905B2 JP 3255642 A JP3255642 A JP 3255642A JP 25564291 A JP25564291 A JP 25564291A JP 2580905 B2 JP2580905 B2 JP 2580905B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- fibers
- fiber
- organic
- base material
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000835 fiber Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 15
- 239000002759 woven fabric Substances 0.000 claims description 13
- 239000012784 inorganic fiber Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000002966 varnish Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 238000000034 method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 8
- 238000005553 drilling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 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
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- HRPWYKJYMAGADJ-UHFFFAOYSA-N C=C.FC(C(F)=C(F)F)(F)F.F.F.F.F Chemical group C=C.FC(C(F)=C(F)F)(F)F.F.F.F.F HRPWYKJYMAGADJ-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 glycol ethers Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Moulding By Coating Moulds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プリプレグの製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a prepreg.
【０００２】[0002]
【従来の技術】回路の信号伝送速度及び伝送損失は基板
の誘電率及び誘電正接に大きく影響される。基板の誘電
率が小さいほどその信号の伝送速度は大きく、又誘電正
接が小さいほど伝送損失は小さくなる。コンピュータな
ど信号伝送速度の高速度化、高効率化が要求される用途
向けの基板は、誘電正接、誘電率共に小さいことが要求
される。2. Description of the Related Art The signal transmission speed and transmission loss of a circuit are greatly affected by the dielectric constant and dielectric loss tangent of a substrate. The transmission rate of the signal is higher as the dielectric constant of the substrate is lower, and the transmission loss is lower as the dielectric loss tangent is lower. Substrates for applications requiring high signal transmission speed and high efficiency, such as computers, are required to have low dielectric loss tangents and dielectric constants.
【０００３】耐熱性有機繊維は、誘電率、誘電正接がガ
ラスに比較して小さいため、耐熱性有機繊維を基材とす
る積層板の誘電率も小さくなる。そこで、プリプレグの
材料として、ガラス繊維基材のほか耐熱性有機繊維基材
が使用されるようになっている。耐熱性有機繊維として
はアラミド繊維、フッ素樹脂繊維、耐熱性エンジニアリ
ングプラスチックと称されるポリエーテルエーテルケト
ンやポリエーテルイミド等の繊維があり、これらを単独
若しくは混合して撚糸した糸、あるいはガラス繊維と前
記の繊維とを混合して撚糸した糸を用いた織布又はこれ
らの繊維を用いた不織布に樹脂を含浸し、乾燥してプリ
プレグとしている。[0003] Since the heat-resistant organic fiber has a smaller dielectric constant and a dielectric loss tangent than glass, the dielectric constant of a laminate made of the heat-resistant organic fiber as a base material also becomes smaller. Therefore, a heat-resistant organic fiber base has been used as a material for the prepreg in addition to the glass fiber base. Examples of heat-resistant organic fibers include aramid fibers, fluororesin fibers, and fibers such as polyetheretherketone and polyetherimide, which are called heat-resistant engineering plastics. A woven fabric using a yarn twisted by mixing with the above-mentioned fibers or a non-woven fabric using these fibers is impregnated with a resin and dried to form a prepreg.
【０００４】ところで、ガラス繊維も耐熱性有機繊維
も、カップリング剤処理、プラズマ処理、金属ナトリウ
ムによる表面処理などを単独又は組み合わせて樹脂との
親和性を高めている。By the way, both glass fibers and heat-resistant organic fibers are improved in affinity with resins by using a coupling agent treatment, a plasma treatment, a surface treatment with metallic sodium, etc., alone or in combination.
【０００５】[0005]
【発明が解決しようとする課題】ところが、カップリン
グ剤処理では、いまだ不充分であり、基材中に樹脂が充
分含浸されず、ボイドを含むため、積層板の耐熱性が悪
くなり、成形に高圧力を必要とする。このため、多層化
接着に使用すると、層間の位置精度が悪くなる。また、
得られた積層板が高温にさらされるとブリスター（界面
剥離）やミーズリング（交絡点の剥離）が発生し、ま
た、多層化する際に寸法安定性が低下してしまうことや
ドリル加工性も悪い。However, the treatment with the coupling agent is still inadequate, the resin is not sufficiently impregnated in the base material and contains voids, so that the heat resistance of the laminated board is deteriorated, and the molding is difficult. Requires high pressure. Therefore, when used for multi-layer bonding, the positional accuracy between layers deteriorates. Also,
When the obtained laminate is exposed to a high temperature, blisters (interfacial peeling) and measling (peeling of entangled points) occur, and the dimensional stability decreases when multi-layering is performed. bad.
【０００６】金属ナトリウムによる表面処理では、取扱
いが困難で、処理しにくい。プラズマ処理する方法は、
真空チャンバを必要とし、また、処理法も複雑なため効
率が悪く、連続的に処理することが困難である。本発明
は、基材と樹脂との親和性を改善する簡便な方法を提供
することを目的とするものである。[0006] Surface treatment with metallic sodium is difficult to handle and difficult to treat. The method of plasma treatment is
Since a vacuum chamber is required and the processing method is complicated, the efficiency is low and it is difficult to continuously process. An object of the present invention is to provide a simple method for improving the affinity between a substrate and a resin.
【０００７】[0007]
【課題を解決するための手段】本発明は、有機繊維又は
有機繊維と無機繊維を複合した織布又は不織布の繊維基
材に紫外線を照射した後、樹脂ワニスを含浸、乾燥する
ことを特徴とする。SUMMARY OF THE INVENTION The present invention provides an organic fiber or
The method is characterized in that, after irradiating ultraviolet rays to a woven or nonwoven fabric base material in which organic fibers and inorganic fibers are combined , a resin varnish is impregnated and dried.
【０００８】繊維基材として、無機繊維ではガラス繊
維、石英繊維が用いられる。有機繊維としては、アラミ
ド樹脂、フッ素樹脂（四フッ化エチレン樹脂、四フッ化
エチレン−六フッ化プロピレン共重合樹脂、四フッ化エ
チレンパーアルキルエーテル共重合樹脂など）耐熱性エ
ンジニアリングプラスチック（全芳香族ポリアミド、ポ
リフェニレンサルファイド、ポリエーテルエーテルケト
ン、ポリエーテルイミド、全芳香族ポリエステルなど）
が挙げられる。要するに、マトリックス樹脂の成形温度
及びはんだ溶融温度に耐えられる繊維であればおおむね
使用可能である。As the fiber base, glass fibers and quartz fibers are used as inorganic fibers. Organic fibers include aramid resin, fluororesin (ethylene tetrafluoride resin, ethylene tetrafluoride-hexafluoropropylene copolymer resin, tetrafluoroethylene peralkyl ether copolymer resin, etc.) and heat-resistant engineering plastics (wholly aromatic) Polyamide, polyphenylene sulfide, polyetheretherketone, polyetherimide, wholly aromatic polyester, etc.)
Is mentioned. In short, it is generally available if Tolerant fibers to the molding temperature and the solder melting temperature of the matrix resin.
【０００９】これらの有機繊維を単独又は有機繊維と無
機繊維を混合したヤーンを平織、綾織、朱子織などの各
種織物とし、あるいは不織布とし、基材として使用す
る。特に無機繊維と有機繊維との混合材が好ましい。繊
維のフィラメント径は、数μｍから数十μｍが好まし
い。このような繊維を複数本合わせて得られるヤーン
を、通常の織物製造と同様にして製織する。この織布の
厚さは、２０μｍないし２５０μｍの範囲のものが望ま
しい。These organic fibers may be used alone or in combination with the organic fibers.
Yarns mixed with machine fibers are used as various woven fabrics such as plain weave, twill weave and satin weave, or as nonwoven fabrics, and used as a base material. Particularly, a mixed material of inorganic fibers and organic fibers is preferable. The filament diameter of the fiber is preferably several μm to several tens μm. The yarn obtained by combining a plurality of such fibers is woven in the same manner as in ordinary woven fabric production. The thickness of the woven fabric is desirably in the range of 20 μm to 250 μm.
【００１０】本発明において、熱硬化性樹脂として、エ
ポキシ樹脂、ポリイミド樹脂、ビスマレイミドートリア
ジシン樹脂、変性ポリイミド樹脂などを使用することが
できるが、誘電率が低いシアネートエステル樹脂、マレ
イミド−スチリル樹脂などが好適である。[0010] In the present invention, as the thermosetting resin, epoxy resin, polyimide resin, bismaleimide over thoria own resin, etc. can be used polyimide resin, the dielectric constant is low cyanate ester resin, a maleimide - styryl tree Fats and the like are preferred.
【００１１】紫外線照射と、カップリング剤処理と組み
合わせてもよい。この場合、カップリング剤で処理した
繊維基材に紫外線を照射してもよく、紫外線を照射した
繊維基材をカップリング剤で処理してもよい。紫外線を
照射した繊維基材をカップリング剤で処理し、さらに紫
外線を照射することも可能である。[0011] UV irradiation and coupling agent treatment may be combined. In this case, the fiber substrate treated with the coupling agent may be irradiated with ultraviolet light, or the fiber substrate irradiated with ultraviolet light may be treated with the coupling agent. It is also possible to treat the fiber substrate irradiated with ultraviolet rays with a coupling agent and further irradiate ultraviolet rays.
【００１２】カップリング剤としては、有機シランを主
成分とするものが広く用いられている。有機シランは、
一般式ＲnＳｉＸ(4-n)で表される。この式において、Ｒ
は少なくとも炭素原子を一つ有する基を表し、炭素原子
に結合する水素原子を、アミノ基、エポキシ基、メルカ
プト基又はビニル基等の反応性を有する基で置換したも
のであってもよい。Ｘは任意の一価の加水分解し得る
基、例えば、ハロゲン原子、アルコキシ基又はアシロキ
シ基を表し、ｎは１〜３の整数である。ｎが１又は２の
とき、Ｘは互いに同一のものでも異なっていてもよい。
有機シランは、二種以上を混合して使用してもよい。As the coupling agent, those containing an organic silane as a main component are widely used. Organosilane is
It is represented by the general formula R n SiX (4-n) . In this formula, R
Represents a group having at least one carbon atom, and the hydrogen atom bonded to the carbon atom is substituted with a reactive group such as an amino group, an epoxy group, a mercapto group, or a vinyl group.
It may be. X represents any monovalent hydrolyzable group, for example, a halogen atom, an alkoxy group or an acyloxy group, and n is an integer of 1 to 3. When n is 1 or 2, Xs may be the same or different.
The organic silane may be used as a mixture of two or more kinds.
【００１３】パーフルオロアルキルシラン（たとえば、
３，３，３−トリフロロプロピルトリメトキシシラン、
３，３−４，４−５，５−６，６−７，７−８，８−ト
リデカフルオロオクチルトリメトキシシラン）、アミノ
シラン（たとえば、γ−（２−アミノエチル）アミノプ
ロピルトリメトキシシラン）のように、繊維基材との親
和性がよいカップリング剤を使用するときは、カップリ
ング剤で処理した後に紫外線を照射し、逆に樹脂との親
和性のよいカップリング剤を使用するときは、紫外線を
照射した後にカップリング剤で処理すれば、効果的であ
る。A perfluoroalkylsilane (for example,
3,3,3-trifluoropropyltrimethoxysilane,
3,3-4,4-5,5-6,6-7,7-8,8-tridecafluorooctyltrimethoxysilane), aminosilane (for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane) When a coupling agent having a good affinity for the fiber base material is used, as in the case of (1), the resin is treated with the coupling agent and then irradiated with ultraviolet rays, and conversely, a coupling agent having a good affinity for the resin is used. In some cases, treatment with a coupling agent after irradiation with ultraviolet rays is effective.
【００１４】有機シランは、通常水溶液又はアルコール
類、ケトン類、グリコールエーテル類などの有機溶剤と
水との混合溶液として、０．０１〜５重量％程度の濃度
に調整して使用される。基材に適用する方法としては、
浸漬法、噴霧法、ガス化法などの、任意の公知の方法が
採用できる。一般に多用される浸漬法は、室温に近い温
度で基材を溶液に数秒浸漬した後、マングルで絞り、続
いて８０〜１８０℃で数分間乾燥キュアリングすること
により、有機シランが０．０１〜２重量％程度付与され
た基材を得ている。The organic silane is usually used as an aqueous solution or a mixed solution of an organic solvent such as alcohols, ketones, glycol ethers and the like and water at a concentration of about 0.01 to 5% by weight. As a method to apply to the substrate,
Any known method such as an immersion method, a spray method, and a gasification method can be adopted. A commonly used immersion method is that a substrate is immersed in a solution at a temperature close to room temperature for several seconds, then squeezed with a mangle, and then dried and cured at 80 to 180 ° C. for several minutes, so that the organic silane is 0.01 to 0.01%. A base material having about 2% by weight is obtained.
【００１５】照射する紫外線としては波長が２００〜４
００ｎｍのものを使用し、紫外線ランプを用い一般に公
知の処理条件が採用される。紫外線ランプとしては１０
０〜１０００ｎｍの波長の光を放出する各種ランプ（例
えば、低圧水銀ランプ、高圧水銀ランプ）が使用でき
る。The ultraviolet light to be irradiated has a wavelength of 200 to 4
A known treatment condition is generally adopted using a UV lamp having a thickness of 00 nm and an ultraviolet lamp. 10 for UV lamp
Various lamps that emit light having a wavelength of 0 to 1000 nm (for example, a low-pressure mercury lamp and a high-pressure mercury lamp) can be used.
【００１６】照射量は、累積で１００ｍＪ／ｃｍ2 〜２
０００ｍＪ／ｃｍ2 の範囲とする。１００ｍＪ／ｃｍ2
に満たないと、効果がない。紫外線照射の効果は、２０
００ｍＪ／ｃｍ2 で飽和し、また、材料により差異はあ
るが、カップリング剤及び有機基材が熱劣化して変質す
るおそれがある。The irradiation amount is 100 mJ / cm 2 to 2 in total.
000 mJ / cm 2 . 100mJ / cm 2
If less than, there is no effect. The effect of UV irradiation is 20
It saturates at 00 mJ / cm 2 , and although different depending on the material, the coupling agent and the organic base material may be thermally deteriorated and deteriorated.
【００１７】[0017]
【作用】紫外線のエネルギーによって基材又はカップリ
ング剤表面の電子状態が不安定となり、空気中の水分、
炭酸ガス、酸素と反応して−ＯＨ、−ＣＯＯＨのような
極性基ができるものと推定される。このため基材−カッ
プリング剤、カップリング剤−樹脂、基材−樹脂の親和
性がよくなり、樹脂の含浸性が向上し、ボイドがなくな
るため、低い圧力での成形が可能となり、従来のプリプ
レグが有していた種々の欠陥がなくなるものと考えられ
る。[Effect] The electronic state of the substrate or the surface of the coupling agent becomes unstable due to the energy of ultraviolet rays, and the moisture in the air,
It is presumed that polar groups such as -OH and -COOH are formed by reacting with carbon dioxide and oxygen. For this reason, the affinity of the base material-coupling agent, the coupling agent-resin, and the base material-resin is improved, the impregnation property of the resin is improved, and voids are eliminated. It is considered that various defects of the prepreg disappear.
【００１８】[0018]
【実施例】実施例１ Ｓガラス繊維６０容量％、四フッ化エチレン樹脂繊維４
０容量％からなる厚み０．１ｍｍの混合織布（６０本／
２５ｍｍ×５８本／２５ｍｍ）をコンベア式紫外線照射
装置で累積照射量が７００ｍＪ／ｃｍ2 （８０Ｗ、１分
間）になるように照射した。次にこの照射処理織布をＮ
−（β−アミノエチル）−γ−アミノプロピルメトキシ
シラン０．１重量％水溶液に浸漬した後、織布１００重
量部に対して水溶液３０重量部になるようにマングルで
均一に絞り、熱風乾燥機で１５０℃にて２分間乾燥し
た。次に、ＮＥＭＡ規格ＦＲ−４のエポキシ樹脂を、織
布５５重量部にたいして、樹脂付着量が４５重量部にな
るように含浸し、プリプレグとした。このプリプレグを
８枚重ねて、１７０℃、圧力２ＭＰａで１時間加圧成形
して積層板とした。得られた積層板の耐熱性は１０時
間、加熱処理（Ｅ−０．５／１７０）後の寸法変化は経
糸方向−０．０４０、緯糸方向−０．０５５であった。
またドリル加工時にクラック又は剥離の発生がなかっ
た。耐熱性は、５０ｍｍ×５０ｍｍの積層板試験片を常
圧で煮沸し、２６０℃のはんだ槽に３０秒浸漬し、取り
出してブリスター、ミーズリングの有無を調べ、ブリス
ターまたはミーズリングが発生する煮沸時間で表す。比
較のため、紫外線照射を除き、外は実施例１と同様にし
て製造した積層板は耐熱性が５時間、加熱処理後の寸法
変化は経糸方向が−０．１１０、緯糸方向が−０．１２
０であった。また、ドリル加工時にクラックまたは剥離
が若干発生した。EXAMPLES Example 1 S glass fiber 60% by volume, ethylene tetrafluoride resin fiber 4
0.1 volume thick mixed woven fabric consisting of 0% by volume (60 /
(25 mm × 58 lines / 25 mm) was irradiated by a conveyor type ultraviolet irradiation apparatus so that the cumulative irradiation amount became 700 mJ / cm 2 (80 W, 1 minute). Next, this irradiated fabric is
After dipping in a 0.1% by weight aqueous solution of-(β-aminoethyl) -γ-aminopropylmethoxysilane, the solution is uniformly squeezed with a mangle so that the aqueous solution becomes 30 parts by weight with respect to 100 parts by weight of a woven fabric. At 150 ° C. for 2 minutes. Next, epoxy resin of NEMA standard FR-4 was impregnated with 55 parts by weight of the woven fabric so that the resin adhesion amount was 45 parts by weight to prepare a prepreg. Eight of these prepregs were stacked and pressed under a pressure of 2 MPa at 170 ° C. for 1 hour to form a laminate. The heat resistance (E-0.5 / 170) of the obtained laminate was 10 hours, and the dimensional change after the heat treatment (E-0.5 / 170) was -0.040 in the warp direction and -0.055 in the weft direction.
No cracking or peeling occurred during drilling. The heat resistance is as follows. A 50 mm × 50 mm laminated plate test piece is boiled at normal pressure, immersed in a solder bath at 260 ° C. for 30 seconds, taken out and checked for blisters and measling, and the boiling time at which blisters or measling occurs. Expressed by For comparison, a laminate manufactured in the same manner as in Example 1 except for the irradiation of ultraviolet light had a heat resistance of 5 hours, and the dimensional change after the heat treatment was -0.110 in the warp direction and -0.110 in the weft direction. 12
It was 0. Further, cracking or peeling occurred slightly during drilling.
【００１９】実施例２ Ｓガラス繊維６０容量％、ポリエーテルエーテルケトン
樹脂繊維４０容量％とからなる厚さ０．１ｍｍの混合織
布（６０本／２５ｍｍ×５８本／２５ｍｍ）を基材とし
以下実施例１と同様にして積層板を得た。得られた積層
板の耐熱性は１１時間であった。加熱処理後の寸法変化
は、経糸方向が−０．０３５、緯糸方向が−０．０４０
であった。またドリル加工時にクラックまたは剥離の発
生がなかった。比較のため、紫外線照射を除き、他は実
施例２と同様にして製造した積層板は耐熱性が６時間、
加熱処理後の寸法変化は経糸方向が−０．１００、緯糸
方向が−０．１０５であった。また、ドリル加工時にク
ラックまたは剥離が若干発生した。 EXAMPLE 2 A 0.1 mm thick mixed woven fabric (60 fibers / 25 mm × 58 fibers / 25 mm) composed of 60 volume% of S glass fiber and 40 volume% of polyetheretherketone resin fiber was used as a base material. A laminate was obtained in the same manner as in Example 1 . The heat resistance of the obtained laminate was 11 hours. The dimensional change after the heat treatment was -0.035 in the warp direction and -0.040 in the weft direction.
Met. No cracking or peeling occurred during drilling. For comparison, the laminates produced in the same manner as in Example 2 except for the irradiation of ultraviolet rays had heat resistance of 6 hours,
The dimensional change after the heat treatment was -0.100 in the warp direction and -0.105 in the weft direction. Further, cracking or peeling occurred slightly during drilling.
【００２０】実施例３ 実施例１において、エポキシ樹脂に代えてマレイミド−
スチリル樹脂を用い以下実施例１と同じ条件で積層板を
得た。得られた積層板の耐熱性は１２時間であった。加
熱処理後の寸法変化は、経糸方向が−０．０３５、緯糸
方向が−０．０４０であった。またドリル加工時にクラ
ックまたは剥離の発生がなかった。比較のため、紫外線
照射を除き、他は実施例３と同様にして製造した積層板
の耐熱性は５時間であった。加熱処理後の寸法変化は、
経糸方向が−０．１１０、緯糸方向が−０．１２０であ
った。また、ドリル加工時にクラックまたは剥離が若干
発生した。 Example 3 In Example 1 , maleimide was used in place of the epoxy resin.
To obtain a laminated board under the same conditions as in Example 1 using a styryl resins. The heat resistance of the obtained laminate was 12 hours. The dimensional change after the heat treatment was -0.035 in the warp direction and -0.040 in the weft direction. No cracking or peeling occurred during drilling. For comparison, the heat resistance of the laminate manufactured in the same manner as in Example 3 except for the irradiation of ultraviolet rays was 5 hours. The dimensional change after heat treatment is
The warp direction was -0.110 and the weft direction was -0.120. Further, cracking or peeling occurred slightly during drilling.
【００２１】実施例４ 四フッ化エチレン樹脂繊維からなる厚み０．１ｍｍの織
布（６０本／２５ｍｍ×５８本／２５ｍｍ）に繊維基材
との親和性の良いγ−（２−アミノエチル）アミノプロ
ピルトリメトキシシラン処理し、次にコンベア式紫外線
照射装置で累積照射量が７００ｍＪ／ｃｍ2 （８０Ｗ、
１分間）になるように照射した。この織布にエポキシ樹
脂を、織布５５重量部に対して、樹脂付着量が４５重量
部になるように含浸し、プリプレグとし、実施例１と同
じ条件で積層板を得た。得られた積層板の耐熱性は８時
間であった。加熱処理後の寸法変化は、経糸方向が−
０．０６０、緯糸方向が−０．０８０であった。また、
ドリル加工時にクラック又は剥離の発生がなかった。比
較のため、紫外線照射を除き、他は実施例４と同様にし
て製造した積層板の耐熱性は３時間であった。加熱処理
後の寸法変化は、経糸方向が−０．１３０、緯糸方向が
−０．１５０であった。また、ドリル加工時にクラック
又は剥離が発生した。 Example 4 A 0.1 mm thick woven fabric (60 fibers / 25 mm.times.58 fibers / 25 mm) made of tetrafluoroethylene resin fiber was applied to .gamma .- (2-aminoethyl) having a good affinity with the fiber base material. Aminopropyltrimethoxysilane treatment, and then a cumulative irradiation amount of 700 mJ / cm 2 (80 W,
(1 minute). This woven fabric was impregnated with an epoxy resin so that the resin adhesion amount was 45 parts by weight with respect to 55 parts by weight of the woven fabric to prepare a prepreg, and a laminate was obtained under the same conditions as in Example 1 . The heat resistance of the obtained laminate was 8 hours. The dimensional change after the heat treatment is
0.060, and the weft direction was -0.080. Also,
No cracking or peeling occurred during drilling. For comparison, the heat resistance of the laminate manufactured in the same manner as in Example 4 except for the irradiation of ultraviolet light was 3 hours. The dimensional change after the heat treatment was -0.130 in the warp direction and -0.150 in the weft direction. In addition, cracking or peeling occurred during drilling.
【００２２】[0022]
【発明の効果】本発明のよれば、樹脂と基材との親和性
がよくなるため、樹脂の基材への含浸性がよくなり、印
刷配線板としての耐熱性、寸法安定性、信頼性が向上す
る。According to the present invention, since the affinity between the resin and the base material is improved, the impregnation property of the resin with the base material is improved, and the heat resistance, dimensional stability and reliability as a printed wiring board are improved. improves.
フロントページの続き (72)発明者 金子 陽一 茨城県下館市大字小川1500番地 日立化 成工業株式会社下館工場内 (72)発明者 鈴木 隆之 茨城県下館市大字小川1500番地 日立化 成工業株式会社下館工場内 (56)参考文献 特開 平４−16530（ＪＰ，Ａ)Continuing from the front page (72) Inventor Yoichi Kaneko 1500 Ogawa, Shimodate-shi, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd. Inside the factory (56) References JP-A-4-16530 (JP, A)
Claims (2)
した織布又は不織布の繊維基材に紫外線を照射した後、
樹脂ワニスを含浸、乾燥することを特徴とするプリプレ
グの製造方法。An organic fiber or a composite of an organic fiber and an inorganic fiber.
After irradiating the woven or non-woven fiber base material with ultraviolet light,
A method for producing a prepreg, comprising impregnating and drying a resin varnish.
有機繊維と無機繊維を複合した織布又は不織布の繊維基
材に紫外線を照射した後、樹脂ワニスを含浸、乾燥する
ことを特徴とするプリプレグの製造方法。2. Organic fibers treated with a coupling agent or
After irradiation with ultraviolet rays of organic fibers and inorganic fibers in the fiber base material of the composite and woven or nonwoven fabric, impregnated with a resin varnish, wherein the to pulp prepreg manufacturing method of drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3255642A JP2580905B2 (en) | 1990-11-08 | 1991-10-03 | Manufacturing method of prepreg |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30332090 | 1990-11-08 | ||
| JP2-303320 | 1990-11-08 | ||
| JP3255642A JP2580905B2 (en) | 1990-11-08 | 1991-10-03 | Manufacturing method of prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05416A JPH05416A (en) | 1993-01-08 |
| JP2580905B2 true JP2580905B2 (en) | 1997-02-12 |
Family
ID=26542341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3255642A Expired - Lifetime JP2580905B2 (en) | 1990-11-08 | 1991-10-03 | Manufacturing method of prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2580905B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0979815A1 (en) * | 1998-08-11 | 2000-02-16 | Lonza A.G. | Unsaturated oligophenolcyanates |
| JP2016056491A (en) * | 2014-09-11 | 2016-04-21 | 倉敷紡績株式会社 | Fiber sheet for fiber-reinforced resin and production method of the same, and molded body using the same and production method of the molded body |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2844840B2 (en) * | 1990-05-10 | 1999-01-13 | 日東紡績株式会社 | Method for producing glass fiber substrate, glass fiber substrate and glass fiber reinforced resin laminate |
-
1991
- 1991-10-03 JP JP3255642A patent/JP2580905B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05416A (en) | 1993-01-08 |
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