JP4667740B2 - Printed wiring board - Google Patents

Printed wiring board Download PDF

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JP4667740B2
JP4667740B2 JP2003409155A JP2003409155A JP4667740B2 JP 4667740 B2 JP4667740 B2 JP 4667740B2 JP 2003409155 A JP2003409155 A JP 2003409155A JP 2003409155 A JP2003409155 A JP 2003409155A JP 4667740 B2 JP4667740 B2 JP 4667740B2
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polyester resin
parts
wiring board
printed wiring
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JP2004207704A (en
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克義 石田
淳 鈴木
喜和子 大森
隆之 今井
博明 渡邉
敦俊 高野
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Fujikura Kasei Co Ltd
Fujikura Ltd
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Fujikura Ltd
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Description

この発明は、フレキシブルプリント基板(FPC)などのプリント配線板の導体回路上に塗布し、導体回路を保護、絶縁するための保護インク混和物に関する。   The present invention relates to a protective ink mixture that is applied onto a conductor circuit of a printed wiring board such as a flexible printed circuit board (FPC) to protect and insulate the conductor circuit.

ポリエチレンテレフタレートなどの基材フィルム上に、銀ペーストなどの導電性ペーストをスクリーン印刷などにより印刷して導体回路を形成し、この導体回路上に絶縁保護層を設けた構造のメンブレンスイッチが知られている。
このようなメンブレンスイッチは、例えばコンピュータ機器、オーディオ機器、ビディオ機器、OA機器などの各種電気機器のスイッチなどとして広く使われている。
A membrane switch having a structure in which an electrically conductive paste such as silver paste is printed on a base film such as polyethylene terephthalate by screen printing to form a conductor circuit and an insulating protective layer is provided on the conductor circuit is known. Yes.
Such membrane switches are widely used as switches for various electric devices such as computer devices, audio devices, video devices, and OA devices.

このメンブレンスイッチの絶縁保護層には、保護インク混和物を塗布し、固化してなるものが主に用いられており、この保護インク混和物としては、基材フィルムとしてポリエチレンテレフタレートフィルムが多く使われていることから、その接着性の点で塩化ビニル樹脂、飽和ポリエステル樹脂、アクリル樹脂などを主成分とする混和物が主に使用されている。   The insulation protective layer of this membrane switch is mainly made by applying a protective ink mixture and solidifying it. As this protective ink mixture, a polyethylene terephthalate film is often used as a base film. Therefore, an admixture mainly composed of a vinyl chloride resin, a saturated polyester resin, an acrylic resin or the like is mainly used from the viewpoint of adhesiveness.

ところで、このようなメンブレンスイッチについては、防災の観点からその構成材料に良好な難燃性が求められており、その絶縁保護層にも難燃性が要求されている。このため、絶縁保護層をなす保護インク混和物として、デカブロモジフェニルエーテルなどのハロゲン系難燃剤を配合したものなどが検討されている。   By the way, about such a membrane switch, the flame retardant property is calculated | required from the viewpoint of disaster prevention, and the flame retardant property is requested | required also for the insulating protective layer. For this reason, a blend of a halogen-based flame retardant such as decabromodiphenyl ether has been studied as a protective ink mixture for forming an insulating protective layer.

しかしながら、この種のハロゲン系難燃剤を添加した難燃性保護インク混和物では、この難燃性保護インク混和物を用いたメンブレンスイッチ等の廃棄焼却処分の際に、有害なハロゲン含有ガスが発生するため、その使用を避けざるを得ないと言う欠点がある。   However, in the flame retardant protective ink blend to which this kind of halogen flame retardant is added, harmful halogen-containing gas is generated during disposal by incineration of membrane switches etc. using this flame retardant protective ink blend. Therefore, there is a drawback that it must be avoided.

このため、水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物などのノンハロゲン系難燃剤を多量に配合することなどが行われている。
しかし、金属水酸化物を大量配合した絶縁保護層では、基材フィルムとの接着性が低下し、耐摺動性や絶縁性が低下するという大きな問題がある。
このような用途に用いられる保護インク混和物に関する先行技術文献としては、例えば以下に示すようなものがある。
特開2002−189289号公報 特開平11−18134号公報
For this reason, a lot of non-halogen flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide are blended.
However, in the insulating protective layer containing a large amount of metal hydroxide, there is a big problem that the adhesion to the base film is lowered, and the sliding resistance and insulation are lowered.
Examples of prior art documents relating to the protective ink mixture used for such applications include the following.
JP 2002-189289 A Japanese Patent Laid-Open No. 11-18134

よって、本発明における課題は、メンブレンスイッチなどのプリント配線板等の絶縁保護層に用いられる保護インク混和物において、基材フィルムに対して接着力が高く、耐摺動性や絶縁性の低下がなく、ノンハロゲンで、十分な難燃性を有する難燃性の保護インク混和物を得ることにある。   Therefore, the problem in the present invention is that, in a protective ink mixture used for an insulating protective layer such as a printed wiring board such as a membrane switch, the adhesive strength to the base film is high, and the sliding resistance and the insulating property are reduced. The object is to obtain a flame-retardant protective ink mixture that is non-halogen and has sufficient flame retardancy.

かかる課題を解決するため、
請求項1にかかる発明は、ポリエチレンテレフタレートからなる絶縁基板上の導体回路上に、保護インク混和物を用いて、保護絶縁膜を形成してなるプリント配線板であって、前記保護インク混和物は、ポリエステル樹脂100重量部と、平均粒子径5μm以下のメラミンシアヌレート60〜150重量部を含み、前記ポリエステル樹脂100重量部は、ガラス転移温度−15℃〜−18℃のポリエステル樹脂60〜80重量部と、ガラス転移温度15℃〜20℃のポリエステル樹脂20〜40重量部を含み、前記ポリエステル樹脂の重量平均分子量は10000〜30000であり、前記メラミンシアヌレートは、その表面が表面処理されていないプリント配線板である。
To solve this problem,
The invention according to claim 1 is a printed wiring board in which a protective insulating film is formed on a conductive circuit on an insulating substrate made of polyethylene terephthalate using a protective ink mixture, and the protective ink mixture is 100 parts by weight of polyester resin and 60 to 150 parts by weight of melamine cyanurate having an average particle size of 5 μm or less, and 100 parts by weight of polyester resin is 60 to 80 parts by weight of polyester resin having a glass transition temperature of −15 ° C. to −18 ° C. Part and 20 to 40 parts by weight of a polyester resin having a glass transition temperature of 15 ° C. to 20 ° C., the weight average molecular weight of the polyester resin is 10,000 to 30,000, and the surface of the melamine cyanurate is not surface-treated. It is a printed wiring board .

請求項2にかかる発明は、前記保護インク混和物が、イソシアネート系硬化剤またはアミン系硬化剤が添加されたものである請求項1に記載のプリント配線板である。 The invention according to claim 2 is the printed wiring board according to claim 1 , wherein the protective ink mixture is one in which an isocyanate curing agent or an amine curing agent is added .

請求項3にかかる発明は、UL規格のVTM−2に合格する請求項1または2に記載のプリント配線板である。 The invention according to claim 3 is the printed wiring board according to claim 1 or 2, which passes UL standard VTM-2.

本発明の保護インク混和物にあっては、良好な接着力を発揮し、高い難燃性を有するものとなり、焼却処分をしても有害なハロゲン含有ガスが発生することもない。また、保護絶縁層の着色を淡くうすい色にすることができ、顧客に違和感を与えることがない。
また、ポリエステル樹脂として、ガラス転移温度−15℃〜−18℃のポリエステル樹脂60〜80重量部と、ガラス転移温度15℃〜20℃のポリエステル樹脂20〜40重量部を含むものを用いた場合には、メラミンシアヌレートを添加することに起因して生じる耐折り曲げ性の低下を防ぐことができ、絶縁基板を折り曲げることにより導体抵抗が上昇したり、保護絶縁膜にクラック、割れが生じることがなくなる。
The protective ink mixture of the present invention exhibits good adhesion and high flame retardancy, and no harmful halogen-containing gas is generated even when incinerated. Moreover, the coloring of the protective insulating layer can be made light and light, and the customer does not feel uncomfortable.
In addition, when a polyester resin containing 60 to 80 parts by weight of a polyester resin having a glass transition temperature of -15 ° C to -18 ° C and 20 to 40 parts by weight of a polyester resin having a glass transition temperature of 15 ° C to 20 ° C is used. Can prevent a decrease in bending resistance caused by the addition of melamine cyanurate, and the conductor resistance is not increased by bending the insulating substrate, and the protective insulating film is not cracked or cracked. .

また、本発明のプリント配線板にあっては、このためその保護絶縁層が良好な接着力を発揮し、UL規格のVTM−2に合格する高い難燃性を有し、耐摺動性も優れたものとなる。また、ノンハロゲンであるので焼却処分をしても有害なハロゲン含有ガスが発生することもない。また、その保護絶縁層は、着色がうすく、外観が優れたものとなる。   Moreover, in the printed wiring board of the present invention, the protective insulating layer exhibits a good adhesive force, has high flame resistance that passes UL standard VTM-2, and has sliding resistance. It will be excellent. In addition, since it is non-halogen, no harmful halogen-containing gas is generated even when incinerated. Further, the protective insulating layer is lightly colored and has an excellent appearance.

以下、本発明をその実施の形態に基づいて、詳しく説明する。
図1および図2は、いずれも本発明のプリント配線板の例を示すもので、図中符号1は、絶縁基板となる基材フィルムを示す。
この基材フィルム1は、ポリエチレンテレフタレート、ポリエチレンナフタレートなどの飽和ポリエステル、ポリイミド、ポリフェニレンスルフィド、ポリエチレン、ポリプロピレン、ポリアミドなどのプラスチックからなる厚み10〜200μmのフィルムである。これらのプラスチックフィルムの中でもポリエチレンテレフタレートフィルムが、電気的特性、機械的特性、コストなどの点でこのましい。
Hereinafter, the present invention will be described in detail based on the embodiments.
1 and 2 each show an example of a printed wiring board of the present invention, and reference numeral 1 in the drawing indicates a base film that serves as an insulating substrate.
The base film 1 is a film having a thickness of 10 to 200 μm made of a saturated polyester such as polyethylene terephthalate or polyethylene naphthalate, a plastic such as polyimide, polyphenylene sulfide, polyethylene, polypropylene, or polyamide. Among these plastic films, polyethylene terephthalate film is preferable in terms of electrical characteristics, mechanical characteristics, cost, and the like.

この基材フィルム1の一方の表面(図1)または両方の表面(図2)には、所望のパターン形状の導体回路2が形成されている。この導体回路2は、銀ペーストなどの導電性ペーストをスクリーン印刷などの印刷法により基材フィルム1上に印刷し、加熱などの固化手段により固化せしめるアディティブ法によって形成されたもので、その厚さが10〜100μm、線幅0.05〜10mm程度のものである。   On one surface (FIG. 1) or both surfaces (FIG. 2) of the base film 1, a conductor circuit 2 having a desired pattern shape is formed. The conductor circuit 2 is formed by an additive method in which a conductive paste such as a silver paste is printed on the base film 1 by a printing method such as screen printing, and is solidified by a solidifying means such as heating. Is about 10 to 100 μm and the line width is about 0.05 to 10 mm.

この導体回路2上には、これを覆うように、厚さ10〜300μmの保護絶縁層3が設けられている。この保護絶縁層3は、少なくとも導体回路2を被覆しておればよく、導体回路2以外の基材フィルム1の一部または全部を被覆していてもよい。なお、必要に応じて、導体回路2と保護絶縁層3とを2層以上積層して複数層の電気回路を基材フィルム1上に形成することもある。
かかる保護絶縁層3は、以下に説明する保護インク混和物を印刷あるいは塗布し、加熱して固化、硬化させてなるものである。
A protective insulating layer 3 having a thickness of 10 to 300 μm is provided on the conductor circuit 2 so as to cover it. This protective insulating layer 3 only needs to cover at least the conductor circuit 2, and may cover a part or all of the base film 1 other than the conductor circuit 2. If necessary, two or more conductor circuits 2 and protective insulating layers 3 may be laminated to form a multi-layer electric circuit on the base film 1.
The protective insulating layer 3 is formed by printing or applying a protective ink mixture described below and solidifying and curing by heating.

ここで用いられる保護インク混和物は、ポリエステル樹脂100重量部と、平均粒子径5μm以下のメラミンシアヌレート60〜150重量部を必須成分として含むものである。   The protective ink mixture used here contains 100 parts by weight of a polyester resin and 60 to 150 parts by weight of melamine cyanurate having an average particle diameter of 5 μm or less as essential components.

上記ポリエステル樹脂としては、テレフタル酸、イソフタル酸、ジフェニルカルボン酸、アジピン酸、コハク酸、サバシン酸などの酸成分と、エチレングリコール、1,4−ブタンジオール、1,4−ジシクロヘキサンジメチロール、ネオペンチルグリコール、ジエチレングリコールなどのアルコール成分を原料として周知の縮重合方法によって得られた各種の飽和ポリエステル樹脂、飽和共重合ポリエステル樹脂が用いられる。   Examples of the polyester resin include acid components such as terephthalic acid, isophthalic acid, diphenylcarboxylic acid, adipic acid, succinic acid, and sabacic acid, ethylene glycol, 1,4-butanediol, 1,4-dicyclohexanedimethylol, neo Various saturated polyester resins and saturated copolyester resins obtained by a known condensation polymerization method using alcohol components such as pentyl glycol and diethylene glycol as raw materials are used.

このポリエステル樹脂は、その重量平均分子量が500〜50000、好ましくは10000〜30000の範囲にあるものが、保護絶縁層3の機械的強度が高くなって好ましい。この分子量の調整は、酸成分とアルコール成分との縮重合反応時の種々の重合条件、例えば重合温度、重合時間、重合圧力、重合触媒の種類などを適宜制御することで行われる。
また、このポリエステル樹脂のガラス転移温度には特に制限はないが、ガラス転移温度が−30℃〜70℃の範囲とすることが得られる保護絶縁層3の機械的強度が高くなり好ましい。
The polyester resin preferably has a weight average molecular weight in the range of 500 to 50,000, preferably 10,000 to 30,000 because the mechanical strength of the protective insulating layer 3 is increased. The molecular weight is adjusted by appropriately controlling various polymerization conditions during the condensation polymerization reaction between the acid component and the alcohol component, such as polymerization temperature, polymerization time, polymerization pressure, and type of polymerization catalyst.
Although this is no particular limitation on the glass transition temperature of the polyester resin, the glass transition temperature in the range of -30 ° C. to 70 ° C. are preferred Nari high mechanical strength of the protective insulating layer 3 to be obtained.

また、ポリエステル樹脂として、その100重量部が、ガラス転移温度−15℃〜−18℃のポリエステル樹脂60〜80重量部と、ガラス転移温度15℃〜20℃のポリエステル樹脂20〜40重量部を含むものを使用することができ、このブレンドポリマーを採用することで、保護絶縁膜が軟らかく、可撓性に富むものとなり、耐折り曲げ性が向上するので好ましい。   In addition, as a polyester resin, 100 parts by weight thereof includes 60 to 80 parts by weight of a polyester resin having a glass transition temperature of −15 ° C. to −18 ° C. and 20 to 40 parts by weight of a polyester resin having a glass transition temperature of 15 ° C. to 20 ° C. It is preferable to use this blend polymer because the protective insulating film is soft and flexible and the bending resistance is improved.

また、このポリエステル樹脂においては、保護インク混和物のプラスチックフィルムからなる基材フィルム1への密着性および耐屈曲性を高めるため、イソシアネート系硬化剤またはアミン系硬化剤などの硬化剤を配合し、バインダをなすポリエステル樹脂のポリマー末端においてこれを架橋することが好ましい。   Further, in this polyester resin, in order to improve the adhesion and bending resistance of the protective ink blend to the base film 1 made of a plastic film, a curing agent such as an isocyanate curing agent or an amine curing agent is blended, It is preferable to crosslink this at the polymer terminal of the polyester resin forming the binder.

この硬化剤の配合量は、バインダをなすポリエステル樹脂100重量部に対して、3〜30重量部、好ましくは5〜20重量部とされ、3重量部未満では密着性増大効果が得られず、30重量部を越えると架橋が進行しすぎて保護絶縁層3の可撓性が低下し、耐屈曲性が低下する。   The blending amount of the curing agent is 3 to 30 parts by weight, preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the polyester resin forming the binder. If it exceeds 30 parts by weight, the crosslinking proceeds excessively, the flexibility of the protective insulating layer 3 is lowered, and the bending resistance is lowered.

本発明の保護インク混和物で用いられる難燃剤としては、メラミンシアヌレートが用いられる。
このメラミンシアヌレートは、ノンハロゲンの難燃剤であり、保護絶縁層3の電気抵抗を低下させないものである。このメラミンシアヌレートには、その表面が表面処理されておらず、かつその平均粒子径が5μm以下のものが用いられる。表面処理されたものではこれを使用したプリント配線板の難燃性(UL規格VTM−2)が不合格となって不都合であり、またその平均粒子径が5μmを越えるものではポリエステル樹脂に対する分散性が低下し、さらに保護絶縁層の塗膜特性の低下による折り曲げ性の低下が生じ、かつ吸湿、浸水による絶縁性の低下が生じて不都合となる。
Melamine cyanurate is used as the flame retardant used in the protective ink blend of the present invention.
This melamine cyanurate is a non-halogen flame retardant and does not lower the electrical resistance of the protective insulating layer 3. As the melamine cyanurate, those whose surface is not surface-treated and whose average particle diameter is 5 μm or less are used. In the case of the surface treatment, the flame retardancy (UL standard VTM-2) of the printed wiring board using this is unacceptable, and in the case where the average particle diameter exceeds 5 μm, the dispersibility to the polyester resin is inconvenient. In addition, the bending property is reduced due to the deterioration of the coating properties of the protective insulating layer, and the insulating property is deteriorated due to moisture absorption and water immersion.

このメラミンシアヌレートの配合量は、ポリエステル樹脂100重量部に対して、図2に示すような基材フィルム1の両面に導体回路2および保護絶縁層3が設けられた形態では、60〜150重量部とされ、図1および図2に示すような基材フィルム1の両面または片面に導体回路2および保護絶縁層3が設けられて形態では、80〜120重量部とされ、60重量部未満では難燃性が不足し、150重量部を超えると接着力が低下し、混練性も低下する。   The blending amount of the melamine cyanurate is 60 to 150 weights in the form in which the conductor circuit 2 and the protective insulating layer 3 are provided on both surfaces of the base film 1 as shown in FIG. 2 with respect to 100 parts by weight of the polyester resin. 1 and 2, in the form in which the conductor circuit 2 and the protective insulating layer 3 are provided on both sides or one side of the base film 1 as shown in FIGS. 1 and 2, the amount is 80 to 120 parts by weight, and less than 60 parts by weight. The flame retardancy is insufficient, and if it exceeds 150 parts by weight, the adhesive strength is lowered and the kneadability is also lowered.

また、本発明の効果を損なわない範囲で、さらに種々の添加剤、例えば有機溶剤、酸化防止剤、金属腐食防止剤、着色剤、各種カップリング剤、架橋剤、架橋助剤、帯電防止剤を適宜添加しても良い。
上記有機溶剤には、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、酢酸エチル、酢酸ブチルなどのエステル類、トルエンなどの芳香族類などが用いられる。
Further, various additives such as an organic solvent, an antioxidant, a metal corrosion inhibitor, a colorant, various coupling agents, a crosslinking agent, a crosslinking aid, and an antistatic agent are added as long as the effects of the present invention are not impaired. You may add suitably.
Examples of the organic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and aromatics such as toluene.

本発明の保護インク混和物は、ポリエステル樹脂100重量部と、メラミンシアヌレート60〜150重量部と必要に応じて他の添加成分とを均一に混合することにより製造することができる。   The protective ink blend of the present invention can be produced by uniformly mixing 100 parts by weight of a polyester resin, 60 to 150 parts by weight of melamine cyanurate, and other additive components as required.

また、本発明の保護インク混和物の形態としては、溶液、ペースト等の形態とすることができ、保護絶縁層3を形成するには、溶液タイプとして、基材フィルム1の導体回路2上にスクリーン印刷などの印刷やバーコートなどによる塗布法により塗布して使用することができる。   Moreover, as a form of the protective ink mixture of the present invention, it can be a form of a solution, a paste or the like. In order to form the protective insulating layer 3, as a solution type, on the conductor circuit 2 of the base film 1 It can be used by being applied by a printing method such as screen printing or a bar coating method.

このような保護インク混和物にあっては、ポリエステル樹脂100重量部と、メラミンシアヌレート60〜150重量部を配合したものであるので、十分な難燃性が得られ、これを焼却処分した際に有害なハロゲン含有化合物を生成することがない。   In such a protective ink blend, since 100 parts by weight of a polyester resin and 60 to 150 parts by weight of melamine cyanurate are blended, sufficient flame retardancy is obtained, and when this is disposed of by incineration Does not produce halogen-containing compounds that are harmful to water.

また、本発明のプリント配線板にあっては、その保護絶縁層3が上記組成の保護インク混和物からなるものであるので、導体回路2および基材フィルム1に対する接着力が高く、絶縁性が高く、被膜自体の機械的特性も優れ、良好な摺動性を示し、高い難燃性を有するものとなり、焼却処分をしても有害なハロゲン含有ガスが発生することもない。   In the printed wiring board of the present invention, since the protective insulating layer 3 is made of a mixture of protective inks having the above composition, the adhesive strength to the conductor circuit 2 and the base film 1 is high, and the insulating property is high. High, excellent mechanical properties of the coating itself, good slidability, high flame retardancy, and no harmful halogen-containing gas is generated even when incinerated.

また、この保護インク混和物は、その難燃性が高いため、例えば厚さ20〜80μmの非難燃ポリエチレンテレフタレートフィルムからなる基材フィルム1上に、メラミンシアヌレートの配合量を60〜150重量部とした混和物を用いて基材フィルム1の両面に厚さ20μm以上の保護絶縁層3を設けたものでは、難燃性がUL94に規定されるVTM−2のレベルを達成する。
また、基材フィルム1の片面のみに同様の厚さの保護絶縁層3を設けたもので、メラミンシアヌレートの配合量を80〜120重量部とした混和物を用いた場合のみ、VTM−2の燃焼試験において、保護絶縁膜を内側として試験をしても、外側として試験しても燃焼試験に合格するレベルの難燃性を発現する。
このため、このプリント配線板は、高い接着性と良好な難燃性を要求されるコンピュータ機器等の配線等に使用できる。
Further, since this protective ink mixture has high flame retardancy, the blending amount of melamine cyanurate is 60 to 150 parts by weight on the base film 1 made of a non-flame retardant polyethylene terephthalate film having a thickness of 20 to 80 μm, for example. In the case where the protective insulating layer 3 having a thickness of 20 μm or more is provided on both surfaces of the base film 1 using the admixture described above, the flame retardancy achieves the level of VTM-2 defined in UL94.
Moreover, VTM-2 is provided only when a protective insulating layer 3 having the same thickness is provided on only one surface of the base film 1 and an admixture having a melamine cyanurate content of 80 to 120 parts by weight is used. In this combustion test, even if the test is performed with the protective insulating film as the inner side or the outer side as the outer test, flame retardance at a level that passes the combustion test is exhibited.
For this reason, this printed wiring board can be used for wiring etc. of computer equipment etc. which require high adhesiveness and good flame retardance.

また、本発明においては、絶縁基板としては、先に例示したプラスチックフィルム以外に、紙・フェノール樹脂、ガラス・エポキシ樹脂などのプラスチック複合板を用いることができ、これ以外の絶縁材料を使用することもできる。
さらに、導体回路として、アディティブ法によるもの以外に、銅箔などの金属箔をエッチングして形成するサブストラクト法で形成したものであってもよい。
In addition, in the present invention, as the insulating substrate, in addition to the plastic film exemplified above, a plastic composite plate such as paper / phenolic resin or glass / epoxy resin can be used, and other insulating materials should be used. You can also.
Furthermore, the conductor circuit may be formed by a subtract method in which a metal foil such as a copper foil is formed by etching in addition to the additive method.

以下、具体例を示す。
(例1)
表1に示した配合組成(重量部)の保護インク混和物を、ジエチレングリコールモノエチルエーテルアセテートからなる溶媒に溶解し、固形分70wt%の保護インク混和物溶液を製造した。
Specific examples are shown below.
(Example 1)
The protective ink mixture having the composition (parts by weight) shown in Table 1 was dissolved in a solvent composed of diethylene glycol monoethyl ether acetate to produce a protective ink mixture solution having a solid content of 70 wt%.

厚さ75μmのポリエチレンテレフタレートフィルムの基材フィルムの両面に、市販の銀ペーストをスクリーン印刷したのち加熱して、厚さ20μmの導体回路を形成した。このものの上に上記保護インク混和物溶液をスクリーン印刷して、加熱、固化して、厚さ40μmの保護絶縁層を設け、図2に示すような両面タイプの構成のプリント配線板を作製した。   A commercially available silver paste was screen-printed on both surfaces of a 75 μm thick polyethylene terephthalate film, and then heated to form a 20 μm thick conductor circuit. The protective ink mixture solution was screen-printed on this, heated and solidified to provide a protective insulating layer having a thickness of 40 μm, and a double-sided type printed wiring board as shown in FIG. 2 was produced.

このようにして得られたプリント配線板について、難燃性(UL94、VTM−2)と、折り曲げ試験(接着性)、密着性試験を測定した。
折り曲げ試験は、プリント配線板を曲げ半径0.5mmで、3回繰り返し折り曲げ、導体回路の断線、浮き、線間絶縁抵抗の低下の有無を測定した。線幅0.4mm、線間0.2mmの模擬導体回路で絶縁抵抗が1×1010Ω以上あるものを合格とした。
The printed wiring board thus obtained was measured for flame retardancy (UL94, VTM-2), bending test (adhesiveness), and adhesion test.
In the bending test, the printed wiring board was repeatedly bent three times with a bending radius of 0.5 mm, and the presence or absence of disconnection or floating of the conductor circuit or a decrease in the insulation resistance between lines was measured. A simulated conductor circuit having a line width of 0.4 mm and a line spacing of 0.2 mm and having an insulation resistance of 1 × 10 10 Ω or more was regarded as acceptable.

密着性試験は、JIS K 5600−5−6に規定されたクロスカット法により行い、分類0〜2であるものを合格とし、分類3〜6であるものを不合格とした。また、分類0とは、カットの縁が完全に完全に滑らかで、どの格子の目にも剥がれがない状態のことである。
結果を表1に示す。
The adhesion test was performed by the cross-cut method defined in JIS K 5600-5-6, and those that were classified as 0 to 2 were accepted, and those that were classified as 3 to 6 were rejected. Moreover, the classification 0 is a state in which the edge of the cut is completely smooth and there is no peeling in any lattice eye.
The results are shown in Table 1.

表1において、「ポリエステル樹脂」は、「バイロンGK−140」(商品名、東洋紡社製、ガラス転移温度15〜20℃、ポリエステル樹脂)100重量部に「コロネート2513」(商品名、日本ポリウレタン工業社製、イソシアネート系硬化剤)を10重量部配合したものを、
「メラミンシアヌレート」は、「MC−860」(商品名、日産化学社製)表面処理されておらない平均粒子径3μmのものを示す。
結果を表1に示す。
In Table 1, “Polyester resin” is “Byron GK-140” (trade name, manufactured by Toyobo Co., Ltd., glass transition temperature 15-20 ° C., polyester resin) and 100 parts by weight “Coronate 2513” (trade name, Nippon Polyurethane Industry). 10 parts by weight of an isocyanate curing agent)
“Melamine cyanurate” indicates “MC-860” (trade name, manufactured by Nissan Chemical Industries, Ltd.) having an average particle diameter of 3 μm which is not surface-treated.
The results are shown in Table 1.

Figure 0004667740
Figure 0004667740

(例2)
表2ないし4に示した配合組成(重量部)の保護インク混和物を、ジエチレングリコールモノエチルエーテルアセテートからなる溶媒に溶解し、固形分70wt%の保護インク混和物溶液を製造した。
(Example 2)
The protective ink blends having the blending compositions (parts by weight) shown in Tables 2 to 4 were dissolved in a solvent comprising diethylene glycol monoethyl ether acetate to produce a protective ink blend solution having a solid content of 70 wt%.

厚さ75μmのポリエチレンテレフタレートフィルムの基材フィルムの片面に、市販の銀ペーストをスクリーン印刷したのち加熱して、厚さ20μmの導体回路を形成した。このものの上に上記保護インク混和物溶液をスクリーン印刷して、加熱、固化して、厚さ40μmの保護絶縁層を設け、図1に示すような構成のプリント配線板を作製した。   A commercially available silver paste was screen-printed on one side of a base film of a polyethylene terephthalate film having a thickness of 75 μm and heated to form a conductor circuit having a thickness of 20 μm. The protective ink mixture solution was screen-printed on this, heated and solidified to provide a protective insulating layer having a thickness of 40 μm, and a printed wiring board having a structure as shown in FIG. 1 was produced.

このようにして得られたプリント配線板について、難燃性(UL94、VTM−2)と、折り曲げ試験1(接着性)、折り曲げ試験2(耐繰り返し曲げ性)、ブロッキング性を測定した。
UL94、VTM−2の燃焼試験では、基材フィルムの両面に保護絶縁膜を形成したものと、片面にのみ保護絶縁膜を形成したものを保護絶縁膜形成面を内側あるいは外側として行った。
The printed wiring board thus obtained was measured for flame retardancy (UL94, VTM-2), bending test 1 (adhesiveness), bending test 2 (repeat bending resistance), and blocking properties.
In the combustion test of UL94 and VTM-2, the protective insulating film formed on both sides of the base film and the protective insulating film formed only on one side were used with the protective insulating film forming surface inside or outside.

折り曲げ試験1は、プリント配線板を曲げ半径0.5mmで、3回繰り返し折り曲げ、導体回路の断線、浮きを確認し、曲げなし状態と曲げ状態での導体抵抗を測定した。線幅0.4mm、線間0.2mmの模擬導体回路で初期の曲げなし状態からの回路抵抗上昇分が5Ω以下のものを合格とした。
折り曲げ試験2は、上記と同様のプリント配線板を曲げ半径0mmで往復5回繰り返し曲げたのち、外観を観察し、保護絶縁膜に割れ、クラックが発生していないものを合格とし、発生していたものを不合格とした。絶縁抵抗が1×1010Ω以上あるものを合格とした。
折り曲げ試験1および2は、図1および図2に記載した片面、両面の両方の構造で実施し、どちらかが不合格になった場合は不合格とした。
In the bending test 1, a printed wiring board was repeatedly bent three times with a bending radius of 0.5 mm, and the conductor circuit was confirmed to be disconnected and lifted, and the conductor resistance in the unbent state and the bent state was measured. A simulated conductor circuit having a line width of 0.4 mm and a line spacing of 0.2 mm and having an increase in circuit resistance from the initial unbent state was 5Ω or less was accepted.
Bending test 2 occurs when a printed wiring board similar to the above is bent 5 times in a reciprocating manner with a bending radius of 0 mm, the appearance is observed, and the protective insulating film is cracked and has no cracks. Was rejected. Those having an insulation resistance of 1 × 10 10 Ω or more were regarded as acceptable.
Bending tests 1 and 2 were carried out with both the single-sided and double-sided structures shown in FIGS. 1 and 2, and when either one failed, the test was rejected.

ブロッキング性は、上述のプリント配線板の50mm×50mmのものを2枚重ね合わせ、荷重5kg/cmを印加した状態で、40℃、95RH%の雰囲気中に7日間放置した後、プリント配線板が自然に剥離できたものを合格とした。そして、図1および図2に示した片面および両面のタイプのもので試験を行い、どちらか一方が不合格の場合を不合格とした。
結果を表2ないし4に示す。
The blocking property was obtained by superposing two 50 mm × 50 mm printed wiring boards described above and leaving them in an atmosphere of 40 ° C. and 95 RH% for 7 days with a load of 5 kg / cm 2 applied. Was accepted as a pass. And it tested by the thing of the single side | surface and double-sided type shown in FIG. 1 and FIG. 2, and the case where either one failed was made disqualified.
The results are shown in Tables 2-4.

表2ないし表4において、「ポリエステル樹脂A」は、「バイロン 550」(商品名、東洋紡績社製、ガラス転移温度−15℃〜−18℃のポリエステル樹脂)で、「ポリエステル樹脂B」は、「バイロンGK−140」(商品名、東洋紡積社製、ガラス転移温度20〜15℃、ポリエステル樹脂)である。硬化剤は、「コロネート2513」(商品名、日本ポリウレタン工業社製、イソシアネート系硬化剤)である、「メラミンシアヌレート」は、「MC−860」(商品名、日産化学社製)表面処理されておらない平均粒子径3μmのものを示す。   In Tables 2 to 4, “Polyester resin A” is “Byron 550” (trade name, manufactured by Toyobo Co., Ltd., polyester resin having a glass transition temperature of −15 ° C. to −18 ° C.), and “Polyester resin B” is “Byron GK-140” (trade name, manufactured by Toyobo Co., Ltd., glass transition temperature 20 to 15 ° C., polyester resin). The curing agent is “Coronate 2513” (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., an isocyanate-based curing agent). The average particle diameter is 3 μm.

Figure 0004667740
Figure 0004667740

Figure 0004667740
Figure 0004667740

Figure 0004667740
Figure 0004667740

本発明にかかるプリント配線板の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the printed wiring board concerning this invention. 本発明にかかるプリント配線板の他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the printed wiring board concerning this invention.

符号の説明Explanation of symbols

1・・・基材フィルム、2・・・導体回路、3・・・保護絶縁層。
DESCRIPTION OF SYMBOLS 1 ... Base film, 2 ... Conductor circuit, 3 ... Protective insulating layer.

Claims (3)

ポリエチレンテレフタレートからなる絶縁基板上の導体回路上に、保護インク混和物を用いて、保護絶縁膜を形成してなるプリント配線板であって、A printed wiring board in which a protective insulating film is formed on a conductor circuit on an insulating substrate made of polyethylene terephthalate, using a protective ink mixture,
前記保護インク混和物は、ポリエステル樹脂100重量部と、平均粒子径5μm以下のメラミンシアヌレート60〜150重量部を含み、前記ポリエステル樹脂100重量部は、ガラス転移温度−15℃〜−18℃のポリエステル樹脂60〜80重量部と、ガラス転移温度15℃〜20℃のポリエステル樹脂20〜40重量部を含み、前記ポリエステル樹脂の重量平均分子量は10000〜30000であり、前記メラミンシアヌレートは、その表面が表面処理されていないプリント配線板。The protective ink blend includes 100 parts by weight of a polyester resin and 60 to 150 parts by weight of melamine cyanurate having an average particle diameter of 5 μm or less. The polyester resin 100 parts by weight has a glass transition temperature of −15 ° C. to −18 ° C. 60 to 80 parts by weight of polyester resin and 20 to 40 parts by weight of polyester resin having a glass transition temperature of 15 to 20 ° C. The weight average molecular weight of the polyester resin is 10,000 to 30,000, and the melamine cyanurate has its surface Is a printed wiring board that is not surface-treated.
前記保護インク混和物が、イソシアネート系硬化剤またはアミン系硬化剤が添加されたものである請求項1に記載のプリント配線板。The printed wiring board according to claim 1, wherein the protective ink mixture is an isocyanate-based curing agent or an amine-based curing agent added thereto. UL規格のVTM−2に合格する請求項1または2に記載のプリント配線板。 The printed wiring board of Claim 1 or 2 which passes VTM-2 of UL specification.
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