JPH1161037A - Resin composition for flexible circuit overcoat - Google Patents
Resin composition for flexible circuit overcoatInfo
- Publication number
- JPH1161037A JPH1161037A JP9219610A JP21961097A JPH1161037A JP H1161037 A JPH1161037 A JP H1161037A JP 9219610 A JP9219610 A JP 9219610A JP 21961097 A JP21961097 A JP 21961097A JP H1161037 A JPH1161037 A JP H1161037A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- molecular weight
- polyol
- per molecule
- isocyanate
- 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
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、特に柔軟性及び硬化時
の低収縮性の点で優れた、熱硬化のフレキシブル回路オ
ーバーコート用樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition for a flexible circuit overcoat, which is particularly excellent in flexibility and low shrinkage during curing.
【0002】[0002]
【従来技術】従来、フレキシブル配線回路の表面保護膜
は、カバーレイフィルムと呼ばれるポリイミドフィルム
をパターンに合わせた金型をつくり打ち抜いたのち、接
着剤を用いて張り付けるタイプや、可とう性を持たせた
紫外線硬化型、または熱硬化型のオーバーコート剤をス
クリーン印刷法により塗布するタイプのものであり、特
に後者は作業性の点で有用であった。これら硬化タイプ
のオーバーコート剤には、主にエポキシ樹脂系、アクリ
ル樹脂系、あるいはこれらの複合系よりなる樹脂組成物
が知られている。これらは、特にブタジエン骨格やシロ
キサン骨格、長鎖脂肪族骨格の導入などの変成を行った
樹脂を主成分とすることが多く、これにより、本来ある
耐熱性や、耐薬品性、電気絶縁性の低下をなるべく押さ
えながら、柔軟性の向上や、硬化収縮による反りの発生
を抑制を行ってきた。しかしながら、近年、電子機器の
軽量小型化に伴いフレキシブル基板も軽薄化が進み、こ
れに伴い、オーバーコートする樹脂組成物の柔軟性や硬
化収縮の影響が、より顕著に現れるようになってきてい
る。このため、硬化タイプのオーバーコート剤では、柔
軟性や硬化収縮による反りの点で、要求性能を満足でき
なくなっているのが現状である。2. Description of the Related Art Conventionally, a surface protective film of a flexible wiring circuit has a type in which a polyimide film called a coverlay film is formed by punching a mold in conformity with a pattern and then punched using an adhesive, or has a flexibility. A UV-curable or thermosetting overcoating agent is applied by screen printing, and the latter is particularly useful in terms of workability. As these curable overcoat agents, resin compositions mainly composed of an epoxy resin, an acrylic resin, or a composite thereof are known. In many cases, these resins are mainly composed of a modified resin such as a butadiene skeleton, a siloxane skeleton, or a long-chain aliphatic skeleton, and thus have inherent heat resistance, chemical resistance, and electrical insulation properties. While suppressing the decrease as much as possible, improvement in flexibility and suppression of warpage due to curing shrinkage have been performed. However, in recent years, as the weight and size of electronic devices have been reduced, the weight of flexible substrates has also been reduced, and with this, the influence of the flexibility and curing shrinkage of the resin composition to be overcoated has become more noticeable. . For this reason, curable overcoat agents cannot satisfy the required performance in terms of flexibility and warpage due to curing shrinkage at present.
【0003】[0003]
【発明が解決しようとする課題】フレキシブル回路用オ
ーバーコート剤の特性として必要な、柔軟性、硬化時の
低収縮性、密着性、電気絶縁性、耐薬品性、耐熱性など
の諸特性を十分に満足できる性能を有する樹脂組成物を
開発することにある。Sufficient properties such as flexibility, low shrinkage during curing, adhesion, electrical insulation, chemical resistance, and heat resistance required for the properties of an overcoat agent for a flexible circuit are sufficient. An object of the present invention is to develop a resin composition having satisfactory performance.
【0004】[0004]
【課題を解決しようとする手段】本発明者らは上記問題
点を解決するため鋭意検討した結果、数平均分子量が1
000〜8000で1分子当たり2〜10個の水酸基を
持つポリオールと、ポリブロックイソシアネートを主成
分とするウレタン樹脂系の樹脂組成物を硬化することよ
り、柔軟性、硬化時の低収縮性、密着性、電気絶縁性、
耐薬品性、耐熱性などの諸特性を十分に満足できる性能
を有する保護膜が得られることを見いだし本発明を完成
させた。すなわち、本発明1は(A)数平均分子量が1
000〜8000で、1分子当たり2〜10個の水酸基
を有するポリオール及び(B)ポリブロックイソシアネ
ートを含有するフレキシブル回路オーバーコート用樹脂
組成物、本発明2は(A)数平均分子量が1000〜8
000で、1分子当たり2〜10個の水酸基を有するポ
リブタジエンポリオール及び(B)数平均分子量が10
00〜8000で、1分子当たり2〜10個のブロック
イソシアネート基を有するポリブタジエンポリブロック
イソシアネートを含有するフレキシブル回路オーバーコ
ート用樹脂組成物である。以下、本発明を詳細に説明す
る。The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the number average molecular weight is 1
Flexibility, low shrinkage at the time of curing, and adhesion by curing a polyol having a molecular weight of 2,000 to 8,000 and having 2 to 10 hydroxyl groups per molecule and a resin composition of a urethane resin based on polyblock isocyanate. Properties, electrical insulation,
The present inventors have found that a protective film having a performance sufficiently satisfying various properties such as chemical resistance and heat resistance can be obtained, and completed the present invention. That is, the present invention 1 has (A) a number average molecular weight of 1
2,000 to 8000, a polyol composition having 2 to 10 hydroxyl groups per molecule and (B) a resin composition for a flexible circuit overcoat containing polyblock isocyanate. The present invention 2 (A) has a number average molecular weight of 1000 to 8
000, a polybutadiene polyol having 2 to 10 hydroxyl groups per molecule and (B) a number average molecular weight of 10
It is a resin composition for flexible circuit overcoat containing polybutadiene polyblock isocyanate having a number of block isocyanate groups of 2 to 10 per molecule in the range of 00 to 8000. Hereinafter, the present invention will be described in detail.
【0005】本発明のフレキシブル回路オーバーコート
用樹脂組成物の成分(A)数平均分子量が1000〜8
000で、1分子当たり2〜10個の水酸基を有するポ
リオールと(B)ポリブロックイソシアネートの含有比
はポリブロックイソシアネートの量がポリオールの水酸
基当量数に対し0.8〜3.5倍当量数である。The resin composition for a flexible circuit overcoat of the present invention has a component (A) having a number average molecular weight of 1,000 to 8,
000, the content ratio of the polyol having 2 to 10 hydroxyl groups per molecule and the (B) polyblock isocyanate is such that the amount of the polyblock isocyanate is 0.8 to 3.5 times the number of hydroxyl equivalents of the polyol. is there.
【0006】数平均分子量が1000〜8000で、1
分子当たり2〜10個の水酸基を有するポリオールは、
耐熱性、耐薬品性などのような剛直性樹脂に見られる特
性と、可とう性、低収縮性など柔軟性樹脂に見られる特
性の両方を付与させるのに重要である。分子量がこの範
囲よりも小さくなる場合や、1分子当たりの水酸基の数
がこの範囲よりも大きくなる場合は、硬化時の架橋密度
が高くなるため、より固い硬化物となり、硬化塗膜の柔
軟性や硬化時の低収縮性に関して十分な物性は得られな
い。一方、分子量がこの範囲よりも大きくなる場合や、
1分子当たりの水酸基の数がこの範囲よりも小さくなる
場合は、硬化時の架橋密度が低くなるため、より柔軟な
硬化物となる反面、硬化塗膜の耐熱性や耐薬品性が著し
く低下する。When the number average molecular weight is 1,000 to 8,000,
Polyol having 2 to 10 hydroxyl groups per molecule,
It is important to impart both the properties found in rigid resin such as heat resistance and chemical resistance and the properties found in flexible resin such as flexibility and low shrinkage. When the molecular weight is smaller than this range, or when the number of hydroxyl groups per molecule is larger than this range, the crosslink density at the time of curing increases, resulting in a harder cured product and the flexibility of the cured coating film. Sufficient physical properties cannot be obtained with regard to low shrinkage during curing and curing. On the other hand, when the molecular weight is larger than this range,
When the number of hydroxyl groups per molecule is smaller than this range, the crosslink density at the time of curing is low, so that the cured product is more flexible, but the heat resistance and chemical resistance of the cured coating film are significantly reduced. .
【0007】ポリオールとしては、数平均分子量が10
00〜8000で、水酸基の数が1分子当たり2〜10
個持つものであるならば、樹脂の構造はどのようなもの
でも良く、例えば、ビニルアルコール、アリルアルコー
ルなど水酸基を有するオレフィンと他のオレフィンを共
重合させたアクリルポリオールや、重合時のモル比をず
らして末端に水酸基を残したポリエステルポリオールや
ポリエーテルポリオール、更には樹脂を変成して水酸基
を導入したポリブタジエンや水酸基末端ポリオレフィン
などで、上記分子量及び水酸基数の条件に該当するもの
は全て含まれる。アクリルポリオールとしてはデスモフ
ェンA665(住友バイエルウレタン(株)社製)、ポ
リエステルポリオールとしては、HM−1(荒川化学工
業(株)社製)、エリーテルUE3320(ユニチカ
(株)社製)、水酸基含有ポリブタジエンとしてはG−
1000、GI−1000、GQ−1000、(日本曹
達(株)社製)、水酸基末端ポリオレフィンとしては、
ポリーテルH(三菱化学(株)社製)などが挙げられ
る。中でも、より柔軟性を付与するためには、水酸基含
有ポリブタジエンを用いることが好ましい。The polyol has a number average molecular weight of 10
The number of hydroxyl groups is 2 to 10 per molecule.
The resin may have any structure, as long as it has one, for example, vinyl alcohol, acrylic polyol obtained by copolymerizing an olefin having a hydroxyl group such as allyl alcohol with another olefin, or a molar ratio at the time of polymerization. Polyester polyols and polyether polyols having a hydroxyl group left at the end by shifting, polybutadiene having a hydroxyl group introduced by denaturing the resin, and hydroxyl group-terminated polyolefins, all of which satisfy the above-mentioned conditions of the molecular weight and the number of hydroxyl groups are included. Desmophen A665 (manufactured by Sumitomo Bayer Urethane Co., Ltd.) as an acrylic polyol; HM-1 (manufactured by Arakawa Chemical Industries, Ltd.); Elitel UE3320 (manufactured by Unitika Ltd.); G-
1000, GI-1000, GQ-1000, (manufactured by Nippon Soda Co., Ltd.), and hydroxyl-terminated polyolefins include:
Polytel H (manufactured by Mitsubishi Chemical Corporation) and the like. Among them, it is preferable to use a hydroxyl group-containing polybutadiene in order to impart more flexibility.
【0008】ポリブロックイソシアネートは、2官能以
上のポリイソシアネートをブロック剤でブロックして得
られるものであり、ポリイソシアネートとしては、トル
エン−2,4−ジイソシアネート、トルエン−2,6−
ジイソシアネート、ヘキサメチレンジイソシアネート、
キシリレンジイソシアネート、ジフェニルメタンジイソ
シアネート、イソホロンジイソシアネートなどのジイソ
シアネートや、イソシアネート基の環化3量化反応を利
用し上記ジイソシアネートを3官能以上にしたものや、
イソシアネート基の一部を種々のポリオールと反応させ
3官能以上にしたものも含まれる。またブロック剤とし
ては、イソシアネート基と反応しうる活性水素を1分子
中に1個だけ有する化合物で、イソシアネート基と反応
した後も170℃以下の温度で再び解離するものが好ま
しく、ε−カプロラクタム、マロン酸ジエチル、アセト
酢酸エチル、アセトオキシム、メチルエチルケトオキシ
ム、フェノール、クレゾールなどが挙げられる。The polyblock isocyanate is obtained by blocking a polyisocyanate having two or more functional groups with a blocking agent. Examples of the polyisocyanate include toluene-2,4-diisocyanate and toluene-2,6-
Diisocyanate, hexamethylene diisocyanate,
Diisocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate, and those obtained by making the above diisocyanate trifunctional or higher using a cyclization trimerization reaction of an isocyanate group,
Also included are those in which a part of the isocyanate group is reacted with various polyols to have three or more functional groups. Further, as the blocking agent, a compound having only one active hydrogen capable of reacting with an isocyanate group in one molecule and dissociating again at a temperature of 170 ° C. or less even after reacting with the isocyanate group is preferable, and ε-caprolactam, Examples include diethyl malonate, ethyl acetoacetate, acetoxime, methyl ethyl ketoxime, phenol, cresol and the like.
【0009】中でも、柔軟性、硬化時の低収縮性をより
高めるためには、ブタジエン骨格を分子内に有するポリ
イソシアネートを上記ブロック剤でブロックしたものが
好ましく、例えば、TP−1002(日本曹達(株)
製)や、HTP−9、HTP−5MLD、ユニマックス
P(以上、出光石油化学(株)製)などが挙げられる。Above all, in order to further increase the flexibility and the low shrinkage during curing, it is preferable to block a polyisocyanate having a butadiene skeleton in the molecule with the above-mentioned blocking agent. For example, TP-1002 (Nippon Soda ( stock)
And HTP-9, HTP-5 MLD, and Unimax P (all manufactured by Idemitsu Petrochemical Co., Ltd.).
【0010】また、本発明は以上の必須要素の他に必要
に応じて、ポリオールとイソシアネートの硬化促進剤
や、充填剤、添加剤、チキソ剤、溶剤等を添加しても差
し支えない。特に、耐折り曲げ性をより向上させるため
にはゴム微粒子を添加することが好ましく、また、下地
の銅回路や、ポリイミド、ポリエステルフィルムなどの
ベース基材、接着剤層との密着性をより向上させるため
にはポリアミド微粒子を添加することが好ましい。In the present invention, in addition to the above essential elements, a curing accelerator for polyol and isocyanate, a filler, an additive, a thixotropic agent, a solvent and the like may be added as necessary. In particular, it is preferable to add rubber fine particles in order to further improve the bending resistance, and also to improve the adhesion with the underlying copper circuit, the base material such as polyimide and polyester film, and the adhesive layer. Therefore, it is preferable to add polyamide fine particles.
【0011】ゴム微粒子としてはアクリロニトリルブタ
ジエンゴム、ブタジエンゴム、アクリルゴムなどのゴム
弾性を示す樹脂に化学的架橋処理を行施し、有機溶剤に
不溶かつ不融とした樹脂の微粒子体であるものならばど
のようなものでも良く、例えば、XER−91(日本合
成ゴム(株)社製)、スタフィロイドAC3355、A
C3832、IM101(以上、武田薬品工業(株)社
製)パラロイドEXL2655、EXL2602(以
上、呉羽化学工業(株)社製)などが挙げられる。ポリ
アミド微粒子としては、ナイロンのような脂肪族ポリア
ミドやケブラーのような芳香族ポリアミド、さらには、
ポリアミドイミドなど、アミド結合を有する樹脂の50
ミクロン以下の微粒子であればどのようなものでも良
く、例えば、VESTOSINT 2070(ダイセルヒュルス
(株)社製)や、SP500(東レ(株)社製)などが
挙げられる。As the rubber fine particles, a resin fine particle made of a resin exhibiting rubber elasticity such as acrylonitrile-butadiene rubber, butadiene rubber, and acrylic rubber is subjected to a chemical crosslinking treatment so as to be insoluble and insoluble in an organic solvent. Any material may be used, for example, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, A
C3832, IM101 (all manufactured by Takeda Pharmaceutical Co., Ltd.), paraloids EXL2655 and EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.) and the like. As polyamide fine particles, aliphatic polyamides such as nylon and aromatic polyamides such as Kevlar, and further,
50 of resin having amide bond such as polyamide imide
Any fine particles of submicron size may be used, and examples thereof include VESTOSINT 2070 (manufactured by Daicel Huls Co., Ltd.) and SP500 (manufactured by Toray Industries, Inc.).
【0012】[0012]
【実施例】以下、本発明に用いられるポリオールとブロ
ックイソシアネートの製造例及び、本発明の実施例を比
較例とともに以下に挙げ、本発明をにより具体的に説明
する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to production examples of polyols and blocked isocyanates used in the present invention and examples of the present invention, together with comparative examples.
【0013】[0013]
<樹脂ワニスEの製造>反応容器にバイロン−200
(OH末端ポリエステル、Mn=約15000、OH当
量=7014g/eq.、固形分100w%:東洋紡績
(株)社製)2250gと、エチルジグリコールアセテ
ート(ダイセル化学工業(株)社製)1833g、イプ
ゾール150(出光石油化学(株)社製)917gを入
れ、130℃に加熱しながら撹拌し、溶解させて樹脂ワ
ニスEを得た。 樹脂ワニスEの性状:Mn=約15000、OH当量
(溶剤含)=15586g/eq.、固形分=45w%<Production of resin varnish E> Byron-200 was added to the reaction vessel.
(OH-terminated polyester, Mn = about 15000, OH equivalent = 7014 g / eq., Solid content 100 w%: manufactured by Toyobo Co., Ltd.) 2250 g, ethyl diglycol acetate (manufactured by Daicel Chemical Industries, Ltd.) 1833 g, 917 g of Ipsol 150 (manufactured by Idemitsu Petrochemical Co., Ltd.) was added, stirred while heating to 130 ° C., and dissolved to obtain a resin varnish E. Properties of resin varnish E: Mn = about 15000, OH equivalent (including solvent) = 15586 g / eq. , Solid content = 45w%
【0014】<樹脂ワニスFの製造>反応容器にHTP
−9(NCO末端ポリブタジエン、NCO当量=467
g/eq.、固形分=100w%:出光石油化学(株)
社製)1000gと、エチルジグリコールアセテート
(ダイセル化学工業(株)社製)216gと、ジブチル
錫ラウレート0.1gを混合し均一に溶解させる。均一
になったところで70℃に昇温し、更に撹拌しながら、
メチルエチルケトオキシム(分子量87.12)224
gを2時間かけて滴下し、更に1時間保持、FT−IR
より2250cm−1のNCOピークの消失が確認され
たところで降温し、樹脂ワニスGを得た。樹脂ワニスG
の性状:NCO当量=672.5g/eq.、固形分=
85w%<Production of Resin Varnish F>
-9 (NCO-terminated polybutadiene, NCO equivalent = 467
g / eq. , Solid content = 100w%: Idemitsu Petrochemical Co., Ltd.
1000 g), 216 g of ethyl diglycol acetate (manufactured by Daicel Chemical Industries, Ltd.) and 0.1 g of dibutyltin laurate are mixed and uniformly dissolved. When it became uniform, the temperature was raised to 70 ° C, and with further stirring,
Methyl ethyl ketoxime (molecular weight 87.12) 224
g was added dropwise over 2 hours and kept for 1 hour, FT-IR
When the disappearance of the NCO peak at 2250 cm -1 was confirmed, the temperature was lowered to obtain a resin varnish G. Resin varnish G
Properties: NCO equivalent = 672.5 g / eq. , Solid content =
85w%
【0015】実施例及び比較例に用いた各成分を以下に
示す。 <A成分:ポリブタジエンポリオール> ・デスモフェンA665(アクリルポリオール、Mn=
約1000、OH当量(溶剤含)=607g/eq.、
固形分=65w%:住友バイエルウレタン(株)社製) ・G−1000(OH末端ポリブタジエン、Mn=約1
500、OH当量=801g/eq.、固形分=100
w%:日本曹達(株)社製) <その他のポリオール> ・樹脂ワニスE(OH末端ポリエステル、Mn=約17
000、OH当量(溶剤含)=15586g/eq.、
固形分=45w%) ・PE555(EO変成ペンタエリスリトール、Mn=
約550、OH当量=138g/eq.、固形分=10
0w%:東邦化学(株)社製) <B成分:ポリブロックイソシアネート> ・LS4265(イソホロンジイソシアネート3量化体
のオキシムブロック、NCO当量(溶剤含)=519g
/eq.、固形分=65w%:住友バイエルウレタン
(株)社製) ・樹脂ワニスG(NCO末端ポリブタジエン、NCO当
量=672.5g/eq.、固形分=85w%) <ゴム微粒子> ・EXR−91(日本合成ゴム(株)社製) <ポリアミド微粒子> ・VESTOSINT 2070 (ダイセルヒュルス(株)社製)The components used in Examples and Comparative Examples are shown below. <A component: polybutadiene polyol> Desmophen A665 (acryl polyol, Mn =
About 1000, OH equivalent (including solvent) = 607 g / eq. ,
Solid content = 65 w%: manufactured by Sumitomo Bayer Urethane Co., Ltd.) G-1000 (OH-terminated polybutadiene, Mn = about 1)
500, OH equivalent = 801 g / eq. , Solid content = 100
w%: manufactured by Nippon Soda Co., Ltd.) <Other polyols>-Resin varnish E (OH-terminated polyester, Mn = about 17)
000, OH equivalent (including solvent) = 15586 g / eq. ,
Solid content = 45 w%) PE555 (EO-modified pentaerythritol, Mn =
About 550, OH equivalent = 138 g / eq. , Solid content = 10
0w%: manufactured by Toho Chemical Co., Ltd. <Component B: polyblock isocyanate> LS4265 (oxime block of trimerized isophorone diisocyanate, NCO equivalent (including solvent) = 519 g)
/ Eq. , Solid content = 65 w%: manufactured by Sumitomo Bayer Urethane Co., Ltd.)-Resin varnish G (NCO-terminated polybutadiene, NCO equivalent = 672.5 g / eq., Solid content = 85 w%) <Rubber fine particles>-EXR-91 ( (Nippon Synthetic Rubber Co., Ltd.) <Polyamide fine particles> ・ VESTOSINT 2070 (Daicel Huls Co., Ltd.)
【0016】<塗膜特性の測定> 硬化収縮による反り量:35mm×60mm×75μ
mのポリイミドフィルム上に25mm×35mm×25
μmで塗布し、硬化後の反り量を測定。 耐折り曲げ性試験:マンドレル試験。1〜1/8イン
チ径の範囲で折り曲げ試験を行う。→表示はクラックの
発生しない最小径を示す。 鉛筆硬度:JIS D0202に準じる。 電気絶縁性:導体幅0.318mmのくし型電極に塗
布し、煮沸1時間後の電気抵抗を測定。 耐薬品性:アセトンあるいはイソプロパノールをしみ
込ませたウエスで、塗膜をラビング。→○:異常なし、
×:塗膜劣化 ハンダ耐熱性:塗膜にフラックスJS−64MS−S
を塗布し、それを260℃のハンダ浴に10秒間浸漬。
→ ○:異常なし、:膨れ発生 耐折り曲げ性:JIS C5016に準じて行った。
折り曲げ面の半径は0.38mmとし、クラックが入る
までの折り曲げ回数を測定。→×:10回以下、△:1
0〜1000回、○:1000〜2000回、◎:20
00回以上 密着性:JIS D0202に準じる。基材として、
銅、ポリイミド、及び、フレキシブル基板の接着剤層上
で行った。→×:0/100〜50/100、△:51
/100〜99/100、○:100/100<Measurement of coating film properties> Warpage due to curing shrinkage: 35 mm x 60 mm x 75 μ
25mm × 35mm × 25 on polyimide film
Apply in μm and measure the amount of warpage after curing. Bending resistance test: Mandrel test. Perform a bending test in the range of 11〜 inch diameter. → The display shows the minimum diameter at which cracks do not occur. Pencil hardness: according to JIS D0202. Electrical insulation: applied to a comb-shaped electrode with a conductor width of 0.318 mm, and measured for electrical resistance one hour after boiling. Chemical resistance: Rubbing the coating film with a cloth impregnated with acetone or isopropanol. → ○: No abnormality
×: Deterioration of coating film Solder heat resistance: Flux JS-64MS-S applied to coating film
And dipped in a 260 ° C. solder bath for 10 seconds.
→ :: No abnormality, swelling occurred Bending resistance: Performed according to JIS C5016.
The radius of the bent surface was 0.38 mm, and the number of bendings before cracking was measured. → ×: 10 times or less, Δ: 1
0 to 1000 times, :: 1000 to 2000 times, :: 20
00 times or more Adhesion: According to JIS D0202. As a base material,
The test was performed on copper, polyimide, and an adhesive layer of a flexible substrate. → ×: 0/100 to 50/100, Δ: 51
/ 100-99 / 100, ○: 100/100
【0017】[0017]
【実施例1ー4】 <硬化性樹脂組成物の調整>前記のポリオール、ポリブ
ロックイソシアネート及び、ゴム微粒子、ポリアミド微
粒子を適宜配合し(表1参照)、更にその他成分とし
て、硬化促進剤としてジブチル錫ラウレート、ダレ防止
剤としてアエロジル200(日本アエロジル(株)社
製)、粘度調整溶剤としてカルビトールアセテートを配
合ごとに適量加えて混合し、3本ロールを用いて混練り
して、試料A1〜5を調整した。この調整した試料A−
1〜5を任意の基材に約25μm厚に塗布し、150℃
×60分の条件で硬化を行い、試験サンプルを作製し
た。 評価結果を表2に示した。本発明の硬化性樹脂組
成物の塗膜は、従来の組成物と比べ反り量が特に小さ
く、柔軟性や、耐薬品性、耐熱性、電気絶縁性、耐折り
曲げ性、密着性にも優れ、各特性が良くバランスしてい
る。Example 1-4 <Preparation of Curable Resin Composition> The above polyol, polyblock isocyanate, rubber fine particles and polyamide fine particles were appropriately blended (see Table 1), and dibutyl was used as a curing accelerator as another component. Tin laurate, Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) as an anti-sagging agent, and carbitol acetate as a viscosity adjusting solvent were added in appropriate amounts for each formulation, mixed, and kneaded using a three-roll mill. 5 was adjusted. This adjusted sample A-
Apply 1 to 5 to an arbitrary substrate to a thickness of about 25 μm,
Curing was performed under the conditions of × 60 minutes to prepare a test sample. Table 2 shows the evaluation results. The coating film of the curable resin composition of the present invention has a particularly small amount of warpage as compared with the conventional composition, flexibility, chemical resistance, heat resistance, electrical insulation, bending resistance, and excellent adhesion. Each characteristic is well balanced.
【0018】[0018]
【比較例1及び2】実施例に準拠し表1に示した配合で
各試料B1及びB2を調整し、評価した。結果を表2に
併せ記載した。Comparative Examples 1 and 2 Samples B1 and B2 were prepared and evaluated according to the formulations shown in Table 1 based on the examples. The results are shown in Table 2.
【0019】[0019]
【表1】 [Table 1]
【0020】[0020]
【表2】 [Table 2]
【0021】[0021]
【発明の効果】実施例に示すように、本発明の樹脂組成
物は、従来の組成物と比べ、特に柔軟性、硬化時の反り
に優れ、かつ、耐薬品性、耐熱性、電気絶縁性、耐折り
曲げ性、密着性に優れた熱硬化性の樹脂組成物であり、
フレキシブル回路のオーバーコート剤として適してい
る。As shown in the examples, the resin composition of the present invention is particularly excellent in flexibility, warpage at the time of curing, and has chemical resistance, heat resistance, and electrical insulation properties as compared with the conventional composition. It is a thermosetting resin composition with excellent bending resistance and adhesion.
Suitable as an overcoat agent for flexible circuits.
Claims (4)
で、1分子当たり2〜10個の水酸基を有するポリオー
ル及び(B)ポリブロックイソシアネートを含有するフ
レキシブル回路オーバーコート用樹脂組成物。(A) a number average molecular weight of 1,000 to 8,000
A resin composition for a flexible circuit overcoat, comprising a polyol having 2 to 10 hydroxyl groups per molecule and (B) a polyblock isocyanate.
で、1分子当たり2〜10個の水酸基を有するポリブタ
ジエンポリオール及び(B)数平均分子量が1000〜
8000で、1分子当たり2〜10個のブロックイソシ
アネート基を有するポリブタジエンポリブロックイソシ
アネートを含有するフレキシブル回路オーバーコート用
樹脂組成物。(A) a number average molecular weight of 1,000 to 8,000
And a polybutadiene polyol having 2 to 10 hydroxyl groups per molecule and (B) a number average molecular weight of 1000 to 1000
8000, a resin composition for a flexible circuit overcoat, comprising a polybutadiene polyblock isocyanate having 2 to 10 blocked isocyanate groups per molecule.
(A)ポリオールの水酸基当量数に対し0.8〜3.5
倍当量数であるとなる請求項1及び2記載のフレキシブ
ル回路オーバーコート用樹脂組成物。3. The amount of (B) the polyblock isocyanate is 0.8 to 3.5 with respect to the hydroxyl equivalent number of the (A) polyol.
3. The resin composition for a flexible circuit overcoat according to claim 1, wherein the resin composition has a double equivalent number.
を含有してなる請求項1乃至3記載のフレキシブル回路
オーバーコート用樹脂組成物。4. The resin composition for overcoating a flexible circuit according to claim 1, wherein the resin composition contains rubber fine particles and / or polyamide fine particles.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9219610A JPH1161037A (en) | 1997-08-14 | 1997-08-14 | Resin composition for flexible circuit overcoat |
TW87112900A TW393494B (en) | 1997-08-14 | 1998-08-05 | Curable resin composition for overcoat of flexible circuit |
EP19980306381 EP0896971B1 (en) | 1997-08-14 | 1998-08-10 | Curable resin composition for overcoat of flexible circuit |
US09/132,073 US6162889A (en) | 1997-08-14 | 1998-08-10 | Curable resin composition for overcoat of flexible circuit |
DE1998627088 DE69827088T2 (en) | 1997-08-14 | 1998-08-10 | A curable resin composition for wrapping a flexible power line |
KR1019980032645A KR100545459B1 (en) | 1997-08-14 | 1998-08-12 | Curable resin compositions for flexible circuit overcoating and thin-film cures thereof |
US09/619,497 US6380343B1 (en) | 1997-08-14 | 2000-07-19 | Curable resin composition for overcoat of flexible circuit |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9219610A JPH1161037A (en) | 1997-08-14 | 1997-08-14 | Resin composition for flexible circuit overcoat |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH1161037A true JPH1161037A (en) | 1999-03-05 |
Family
ID=16738234
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9219610A Pending JPH1161037A (en) | 1997-08-14 | 1997-08-14 | Resin composition for flexible circuit overcoat |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH1161037A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000186248A (en) * | 1998-10-15 | 2000-07-04 | Ajinomoto Co Inc | Resin composition for flexible circuit over-coating |
JP2006156452A (en) * | 2004-11-25 | 2006-06-15 | Ube Ind Ltd | Flexible wiring board for tape carrier package with improved burning resistance |
WO2009051209A1 (en) * | 2007-10-18 | 2009-04-23 | Ajinomoto Co., Inc. | Resin composition |
JP2010106067A (en) * | 2008-10-28 | 2010-05-13 | Showa Denko Kk | Polyurethane-based curable composition |
JP2019507817A (en) * | 2016-02-26 | 2019-03-22 | フィナ テクノロジー,インコーポレイティド | Modified polymer and stable emulsion comprising said modified polymer |
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JPS61108671A (en) * | 1984-11-02 | 1986-05-27 | Hitachi Chem Co Ltd | Insulating coating |
JPS61120821A (en) * | 1984-11-16 | 1986-06-07 | Asahi Chem Ind Co Ltd | Composition for forming electrical insulating polyurethane resin |
JPH0328218A (en) * | 1989-06-27 | 1991-02-06 | Hitachi Chem Co Ltd | Urethane resin composition and preparation of moisture-proof insulated packaged circuit board |
JPH0413713A (en) * | 1990-05-02 | 1992-01-17 | Idemitsu Petrochem Co Ltd | Polyurethane composition |
JPH0525433A (en) * | 1991-05-10 | 1993-02-02 | Asahi Chem Ind Co Ltd | Extensible low-temperature-curable one-component polyurethane coating composition |
JPH05320307A (en) * | 1992-05-20 | 1993-12-03 | Idemitsu Petrochem Co Ltd | Liquid polymer composition |
JPH08283659A (en) * | 1995-04-07 | 1996-10-29 | Fujikura Ltd | Urethane varnish |
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1997
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Publication number | Priority date | Publication date | Assignee | Title |
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JPS61108671A (en) * | 1984-11-02 | 1986-05-27 | Hitachi Chem Co Ltd | Insulating coating |
JPS61120821A (en) * | 1984-11-16 | 1986-06-07 | Asahi Chem Ind Co Ltd | Composition for forming electrical insulating polyurethane resin |
JPH0328218A (en) * | 1989-06-27 | 1991-02-06 | Hitachi Chem Co Ltd | Urethane resin composition and preparation of moisture-proof insulated packaged circuit board |
JPH0413713A (en) * | 1990-05-02 | 1992-01-17 | Idemitsu Petrochem Co Ltd | Polyurethane composition |
JPH0525433A (en) * | 1991-05-10 | 1993-02-02 | Asahi Chem Ind Co Ltd | Extensible low-temperature-curable one-component polyurethane coating composition |
JPH05320307A (en) * | 1992-05-20 | 1993-12-03 | Idemitsu Petrochem Co Ltd | Liquid polymer composition |
JPH08283659A (en) * | 1995-04-07 | 1996-10-29 | Fujikura Ltd | Urethane varnish |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000186248A (en) * | 1998-10-15 | 2000-07-04 | Ajinomoto Co Inc | Resin composition for flexible circuit over-coating |
JP2006156452A (en) * | 2004-11-25 | 2006-06-15 | Ube Ind Ltd | Flexible wiring board for tape carrier package with improved burning resistance |
WO2009051209A1 (en) * | 2007-10-18 | 2009-04-23 | Ajinomoto Co., Inc. | Resin composition |
JP5392088B2 (en) * | 2007-10-18 | 2014-01-22 | 味の素株式会社 | Resin composition |
JP2010106067A (en) * | 2008-10-28 | 2010-05-13 | Showa Denko Kk | Polyurethane-based curable composition |
JP2019507817A (en) * | 2016-02-26 | 2019-03-22 | フィナ テクノロジー,インコーポレイティド | Modified polymer and stable emulsion comprising said modified polymer |
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