JP2007277540A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having excellent defoaming property in printing and leveling property without using a silicone-based defoaming agent and giving a protecting film having excellent adhesiveness to substrate, low-warping property, flexibility, metal plating resistance, soldering heat-resistance and long-term reliability under hot and humid condition. <P>SOLUTION: The thermosetting resin composition contains (A) 20-90 mass% thermosetting resin, (B) 10-80 mass% inorganic fine particles and/or organic fine particles and (C) 0.1-5 mass% fluorine-containing polyether. The fluorine-containing polyether of the composition contains a polymer containing one of fluorinated alkyl polyoxetane structures or a copolymer composed of the monomer containing the fluorinated alkyl polyoxetane structure and a 2-6C oxygen-containing monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in defoaming and leveling properties during printing without using a silicone-based antifoaming agent, adhesion to the substrate, low warpage, flexibility, plating resistance, solder heat resistance, Paste thermosetting resin composition for overcoat that gives flexible circuit board with excellent long-term reliability at high temperature and high humidity, overcoat agent using the same, surface protective film comprising the overcoat agent, and for permanent insulation The present invention relates to a protective film ink, a cured product thereof, and an electronic component including the cured product.

  Conventionally, the surface protection film for flexible wiring circuits has a type that adheres an insulating protective film (such as a polyimide film) called a coverlay film to a mold that matches the pattern, and has flexibility. A type in which an applied ultraviolet curable or thermosetting overcoat agent is applied by a screen printing method is used, and the latter thermosetting overcoat agent is particularly excellent in terms of workability.

  As such a thermosetting overcoat agent, a resin composition mainly composed of an epoxy resin system, an acrylic resin system, or a composite system thereof is known. These are often mainly composed of a resin composition which has been modified by introducing a butadiene skeleton, a siloxane skeleton, a polycarbonate diol skeleton, a long-chain aliphatic skeleton, etc. While suppressing the deterioration of the heat resistance, chemical resistance, and electrical insulation provided as much as possible, the flexibility can be improved and the occurrence of warpage due to curing shrinkage can be suppressed.

  However, in recent years, with the reduction in the thickness of flexible substrates accompanying the reduction in weight and size of electronic devices, the effects of the flexibility and curing shrinkage of the resin composition to be overcoated are becoming more prominent. For this reason, the conventional curing-type overcoat agent is currently unable to satisfy the required performance in terms of warping due to flexibility and curing shrinkage.

  When air is entrained when preparing such a paste-like resin composition for a surface protective film, fine bubbles (bubbles) are generated in the paste, causing voids or pinholes. In order to prevent this, it is common to add a small amount of a silicone-based antifoaming agent to the paste-like resin composition. These silicone-based antifoaming agents have an excellent defoaming action, and the amount of bubbles contained in the protective resin paste resin composition can be greatly reduced, preventing the formation of voids or pinholes. It is extremely effective to do this.

  However, silicone antifoaming agents have low compatibility with other resins and high heat resistance. For this reason, when a device is mounted on a flexible substrate, and the whole is sealed with resin and cured by heating, a silicone-based antifoaming agent may ooze out on the surface of the protective film resin and the sealing resin may be repelled. There is a problem that the bonded device cannot be completely sealed.

  Moreover, when the silicone-based antifoaming agent oozes out and adheres to the inner lead surface or the like when the protective resin paste resin composition is cured, it is not only difficult to remove, but also the inner lead and the bump of the device. Connection failure is likely to occur.

  In order to solve these problems, Japanese Patent Application Laid-Open No. 2001-59071 (Patent Document 1) uses a rotation and revolution type stirring device, so that pinholes and the like can be formed without using a silicone-based antifoaming agent. Disclosed is a solder resist coating solution that is difficult to perform. However, with this technique, bubbles remain when the conditions deviate even a little, which is a major obstacle to industrial implementation.

  Actually, it is extremely difficult to defoam bubbles in the paste-like resin composition without using a silicone-based antifoaming agent. Japanese Patent Application Laid-Open No. 2003-327913 (Patent Document 2) or Japanese Patent Application Laid-Open No. 2004-2004 Research on how to reduce the amount of the silicone-based antifoaming agent, as described in Japanese Patent No. 124015 (Patent Document 3), is a drastic improvement measure. Not.

JP 2001-59071 A JP 2003-327913 A JP 2004-124015 A

  The present invention is excellent in defoaming and leveling properties during printing without using a silicone-based antifoaming agent, adhesion to the substrate, low warpage, flexibility, plating resistance, solder heat resistance, The present invention relates to a paste-like thermosetting resin composition, an overcoat agent, and a surface protective film that are excellent in long-term reliability at high temperature and high humidity.

  As a result of intensive studies to solve the various problems described above, the present inventors have found that the above problems can be solved by including a surfactant containing specific fluorine in the paste-like resin composition. In particular, by combining a specific carboxyl group-containing urethane resin and an epoxy resin as a thermosetting resin, a paste-like resin composition for a protective film having a very flexible and good electrical insulation performance can be obtained.

（式中、ｍは１〜１００の整数を表し、ｎは１〜６の整数を表し、Ｒ¹は水素又は炭素数１〜６のアルキル基を表し、Ｒ²及びＲ³はそれぞれ独立して、炭素数１〜２０の直鎖又は分岐鎖のアルキル基を表す。ただし、該アルキル基中の水素原子の少なくとも５０％がフッ素原子で置換され、残りは水素原子もしくはヨウ素原子、塩素原子又は臭素原子で置換されている。）
で表されるフッ素化アルキルポリオキセタン構造のいずれかを含むポリマー、又は該フッ素化アルキルポリオキセタン構造を含むモノマーと炭素数２〜６の酸素原子を含むモノマーからなるコポリマーを含む組成物である、前記１〜３のいずれかに記載の熱硬化性樹脂組成物。
５．前記４中の一般式（１）及び（２）中のｍが２〜３０の整数を表す、前記１〜４のいずれかに記載の熱硬化性樹脂組成物。
６．前記４中の一般式（１）及び（２）中のＲ²及びＲ³で示される炭素数１〜２０の直鎖又は分岐鎖のアルキル基中の水素原子のうち、少なくとも７５％がフッ素原子で置換されている前記１〜５のいずれかに記載の熱硬化性樹脂組成物。
７．前記４中の一般式（１）及び（２）中、ｍは２〜３０の整数を表し、ｎは１〜３の整数を表し、Ｒ¹はメチル基又はエチル基を表し、Ｒ²及びＲ³は直鎖又は分岐状の炭素数１〜７のアルキル基を表し、該アルキル基中の水素原子の少なくとも９５％がフッ素で置換されている、前記１〜６のいずれかに記載の熱硬化性樹脂組成物。
８．（Ｃ）フッ素含有ポリエーテルの数平均分子量が３００〜１００００である前記１〜７のいずれかに記載の熱硬化性樹脂組成物。
９．熱硬化性樹脂（Ａ）が、エポキシ系樹脂、エポキシ系樹脂のエラストマー変性物、ウレタン樹脂、ウレタン樹脂のエラストマー変性物、ポリイミド樹脂及びポリイミド樹脂のエラストマー変性物及びそれらのアクリル酸変性物よりなる群から選ばれる少なくとも一種類の樹脂成分を含有する前記１〜８のいずれかに記載の熱硬化性樹脂組成物。
１０．熱硬化性樹脂（Ａ）が、以下の原料を反応させて得られるカルボキシル基含有ウレタン樹脂を含有する前記１〜９のいずれかに記載の熱硬化性樹脂組成物。
（ａ）ポリイソシアネート化合物、
（ｂ）ポリオール化合物、
（ｃ）カルボキシル基を有するジヒドロキシ化合物、
更に必要に応じて
（ｄ）モノヒドロキシ化合物、及び
（ｅ）モノイソシアネート化合物。
１１．成分（ａ）ジイソシアネート化合物、成分（ｂ）ポリカーボネートジオール、成分（ｃ）ジヒドロキシ化合物、成分（ｄ）モノヒドロキシ化合物及び成分（ｅ）モノイソシアネート化合物の仕込みモル比が、
（ａ）：（（ｂ）＋（ｃ））＝０．５〜１．５：１であり、
（ｂ）：（ｃ）＝１：０．１〜３０であり、
更に、（ｄ）を用いる場合には、（（ｂ）＋（ｃ））≦（ａ）、好ましくは（ｄ）をＮＣＯ基の過剰モル数に対して０．５〜１．５倍モル量とし、
（ｅ）を用いる場合には、（ａ）＜（（ｂ）＋（ｃ））、かつ水酸基の過剰モル数に対して０．５〜１．５倍モル量とする前記１０に記載の熱硬化性樹脂組成物。
１２．成分（ａ）ジイソシアネート化合物、成分（ｂ）ポリカーボネートジオール、成分（ｃ）ジヒドロキシ化合物、成分（ｄ）モノヒドロキシ化合物及び成分（ｅ）モノイソシアネート化合物の仕込みモル比が、
（ａ）：（（ｂ）＋（ｃ））＝０．８〜１．２：１であり、
（ｂ）：（ｃ）＝１：０．３〜１０であり、
更に、（ｄ）を用いる場合には、（（ｂ）＋（ｃ））≦（ａ）、好ましくは（ｄ）をＮＣＯ基の過剰モル数に対して、０．８〜１．２倍モル量とし、
（ｅ）を用いる場合には、（ａ）＜（（ｂ）＋（ｃ））、かつ水酸基の過剰モル数に対して、０．８〜１．２倍モル量とする前記１１に記載の熱硬化性樹脂組成物。
１３．前記１０記載のカルボキシル基含有ウレタン樹脂のポリイソシアネート化合物（ａ）が、１，４−シクロヘキサンジイソシアネート、イソホロンジイソシアネート、メチレンビス（４−シクロヘキシルイソシアネート）、シクロヘキサン−１，３−ジメチレンジイソシアネート及びシクロヘキサン−１，４−ジメチレンジイソシアネートからなる群より選ばれる少なくとも１種の化合物である前記１０〜１２のいずれかに記載の熱硬化性樹脂組成物。
１４．前記１０記載のポリオール化合物（ｂ）が、ポリカーボネートポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリラクトンポリオール、ポリブタジエンポリオール、両末端水酸基化ポリシリコーン、水酸基中以外は酸素を含まず構成成分の炭素数が１８〜７２であるポリオール化合物からなる群より選ばれる少なくとも一種の化合物である前記１０〜１３のいずれかに記載の熱硬化性樹脂組成物。
１５．前記１０記載のカルボキシル基を有するジヒドロキシ化合物（ｃ）が、２，２−ジメチロールプロピオン酸又は２，２−ジメチロールブタン酸である前記１０〜１４のいずれかに記載の熱硬化性樹脂組成物。
１６．前記１０記載のモノヒドロキシ化合物（ｄ）が、２−ヒドロキシエチルアクリレート及び２−ヒドロキシエチルメタアクリレート（以下両者を合わせて２−ヒドロキシエチル（メタ）アクリレートと記す。）、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、シクロヘキサンジメタノールモノ(メタ)アクリレート、前記各（メタ）アクリレートのカプロラクトン又は酸化アルキレン付加物、グリセリンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリルレート、アリルアルコール、アリロキシエタノール、１，４−ブタンジオールモノビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、グリコール酸、ヒドロキシピバリン酸、乳酸、リンゴ酸、クエン酸、２−ヒドロキシエチルプロピオン酸、ヒドロキシイソ酪酸もしくはメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール及びｔ−ブタノール、アミルアルコール、ヘキシルアルコール、オクチルアルコールからなる群より選ばれる少なくとも１種の化合物である前記１０〜１５のいずれかに記載の熱硬化性樹脂組成物。
１７．前記１０記載のモノイソシアネート化合物（ｅ）が、（メタ）アクリロイルオキシエチルイソシアネート、ジイソシアネート化合物に対する２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、シクロヘキサンジメタノールモノ(メタ)アクリレート、前記各（メタ）アクリレートのカプロラクトン又は酸化アルキレン付加物、グリセリンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリルレート、アリルアルコール、アリロキシエタノールのモノ付加体からなる群より選ばれる少なくとも１種の化合物である前記１０〜１６のいずれかに記載の熱硬化性樹脂組成物。
１８．カルボキシル基含有ウレタン樹脂の数平均分子量が１０００〜１０００００であり、かつ、酸価が５〜１２０ｍｇ−ＫＯＨ／ｇである前記１０〜１７のいずれかに記載の熱硬化性樹脂組成物。
１９．カルボキシル基含有ウレタン樹脂の数平均分子量が３０００〜５００００であり、かつ、酸価が１０〜７０ｍｇ−ＫＯＨ／ｇである前記１８に記載の熱硬化性樹脂組成物。
２０．カルボキシル基含有ウレタン樹脂に対して、硬化剤としてポリエポキシ化合物を含有させる前記１０〜１９のいずれかに記載の熱硬化性樹脂組成物。
２１．硬化剤が、ビスフェノール−Ａ、ビスフェノール−Ｆ及び／又はその水添タイプのエポキシ樹脂である前記２０に記載の熱硬化性樹脂組成物。
２２．硬化剤が、脂環式エポキシ化合物である前記２１に記載の熱硬化性樹脂組成物。
２３．前記１に記載の（Ｂ）無機及び／又は有機微粒子が、無機微粒子としてはシリカ、アルミナ、酸化チタン、硫酸バリウム、タルク、炭酸カルシウム、ガラス粉、石英粉、及び、有機微粒子としてはエポキシ樹脂粉末、メラミン樹脂粉末、尿素樹脂粉末、グアナミン樹脂粉末、ポリエステル樹脂粉末、シリコーンパウダーからなる群から選ばれる少なくとも１種の化合物を、熱硬化性樹脂組成物全体に対して５〜４０質量％の割合で配合する前記１〜２２のいずれかに記載の熱硬化性樹脂組成物。
２４．前記1に記載の（Ｃ）フッ素含有ポリエーテルが、エポキシ化合物、オキセタン化合物及び／又はテトラヒドロフラン誘導体とフルオロオキセタンとの共重合体である前記１〜２３のいずれかに記載の熱硬化性樹脂組成物。
２５．前記１〜２４のいずれかに記載の熱硬化性樹脂組成物を含有するフレキシブル基板用のオーバーコート剤。
２６．前記２５に記載のオーバーコート剤からなるフレキシブル基板用の表面保護膜。
２７．前記１〜２６のいずれかに記載の熱硬化性樹脂組成物を含有する永久絶縁保護膜用インキ。
２８．前記２７に記載の永久絶縁保護膜用インキを硬化させてなる硬化物。
２９．前記２８に記載の硬化物を含む電子部品。 That is, the present invention relates to the following [1] to [29].
1. A thermosetting resin composition containing the following components (A), (B) and (C).
(A) thermosetting resin,
(B) inorganic fine particles and / or organic fine particles, and (C) fluorine-containing polyether.
2. Component (A) thermosetting resin, component (B) inorganic fine particles and / or organic fine particles, and component (C) fluorine-containing polyether with respect to the total amount of the thermosetting resin composition (A) thermosetting resin 20-90% by mass,
(B) 10-80% by mass of inorganic fine particles and / or organic fine particles, and (C) 0.1-5% by mass of fluorine-containing polyether,
2. The thermosetting resin composition as described in 1 above, formulated at a ratio of
3. Component (A) thermosetting resin, component (B) inorganic fine particles and / or organic fine particles, and component (C) fluorine-containing polyether with respect to the total amount of the thermosetting resin composition (A) thermosetting resin 40-90% by mass,
(B) 10-60 mass% of inorganic fine particles and / or organic fine particles, and (C) 0.1-5 mass% of fluorine-containing polyether,
3. The thermosetting resin composition as described in 2 above, blended at a ratio of
4). (C) The fluorine-containing polyether is represented by the following general formula (1) or (2)

(In the formula, m represents an integer of 1 to 100, n represents an integer of 1 to 6, R ¹ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ each independently represent Represents a linear or branched alkyl group having 1 to 20 carbon atoms, provided that at least 50% of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the rest are hydrogen atoms, iodine atoms, chlorine atoms or bromine. Substituted with atoms.)
A polymer comprising any one of the fluorinated alkylpolyoxetane structures represented by: or a copolymer comprising a monomer comprising the fluorinated alkylpolyoxetane structure and a monomer comprising an oxygen atom having 2 to 6 carbon atoms, The thermosetting resin composition according to any one of 1 to 3 above.
5). The thermosetting resin composition according to any one of 1 to 4, wherein m in the general formulas (1) and (2) in 4 represents an integer of 2 to 30.
6). At least 75% of the hydrogen atoms in the linear or branched alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ in the general formulas (1) and (2) in 4 are fluorine atoms. The thermosetting resin composition according to any one of 1 to 5, which is substituted with:
7). In the general formulas (1) and (2) in 4 above, m represents an integer of 2 to 30, n represents an integer of 1 to 3, R ¹ represents a methyl group or an ethyl group, R ² and R ³ represents a linear or branched alkyl group having 1 to 7 carbon atoms, and at least 95% of the hydrogen atoms in the alkyl group are substituted with fluorine; Resin composition.
8). (C) The thermosetting resin composition according to any one of 1 to 7, wherein the fluorine-containing polyether has a number average molecular weight of 300 to 10,000.
9. The group in which the thermosetting resin (A) is composed of an epoxy resin, an elastomer modified product of an epoxy resin, a urethane resin, an elastomer modified product of a urethane resin, a polyimide resin, an elastomer modified product of a polyimide resin, and an acrylic acid modified product thereof. The thermosetting resin composition according to any one of 1 to 8 above, which contains at least one resin component selected from:
10. The thermosetting resin composition according to any one of 1 to 9, wherein the thermosetting resin (A) contains a carboxyl group-containing urethane resin obtained by reacting the following raw materials.
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
Further, as necessary (d) a monohydroxy compound, and (e) a monoisocyanate compound.
11. The charged molar ratio of component (a) diisocyanate compound, component (b) polycarbonate diol, component (c) dihydroxy compound, component (d) monohydroxy compound and component (e) monoisocyanate compound is
(A): ((b) + (c)) = 0.5 to 1.5: 1,
(B) :( c) = 1: 0.1-30,
Further, when (d) is used, ((b) + (c)) ≦ (a), preferably (d) is 0.5 to 1.5 times the molar amount relative to the excess number of moles of NCO groups. age,
When (e) is used, (a) <((b) + (c)) and the heat described in 10 above, wherein the molar amount is 0.5 to 1.5 times the molar excess of the hydroxyl group. Curable resin composition.
12 The charged molar ratio of component (a) diisocyanate compound, component (b) polycarbonate diol, component (c) dihydroxy compound, component (d) monohydroxy compound and component (e) monoisocyanate compound is
(A): ((b) + (c)) = 0.8 to 1.2: 1,
(B) :( c) = 1: 0.3-10,
Further, when (d) is used, ((b) + (c)) ≦ (a), preferably (d) is 0.8 to 1.2 moles relative to the excess number of moles of NCO groups. Amount and
When (e) is used, (a) <((b) + (c)), and the molar amount of 0.8 to 1.2 times the molar excess of the hydroxyl group, Thermosetting resin composition.
13. The polyisocyanate compound (a) of the carboxyl group-containing urethane resin described in 10 above is 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate and cyclohexane-1, The thermosetting resin composition according to any one of 10 to 12, which is at least one compound selected from the group consisting of 4-dimethylene diisocyanate.
14 The polyol compound (b) described in 10 is a polycarbonate polyol, a polyether polyol, a polyester polyol, a polylactone polyol, a polybutadiene polyol, a hydroxylated polysilicon at both ends, and contains no oxygen except in the hydroxyl group and has 18 carbon atoms as a constituent component. The thermosetting resin composition according to any one of the above 10 to 13, which is at least one compound selected from the group consisting of polyol compounds of .about.72.
15. 15. The thermosetting resin composition according to any one of 10 to 14, wherein the dihydroxy compound (c) having a carboxyl group as described in 10 is 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid. .
16. The monohydroxy compound (d) described in 10 above is composed of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, both are referred to as 2-hydroxyethyl (meth) acrylate), hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxyethanol, 1,4-butane All monovinyl ether, cyclohexanedimethanol monovinyl ether, glycolic acid, hydroxypivalic acid, lactic acid, malic acid, citric acid, 2-hydroxyethylpropionic acid, hydroxyisobutyric acid or methanol, ethanol, n-propanol, isopropanol, n-butanol, 16. The thermosetting resin composition according to any one of 10 to 15, which is at least one compound selected from the group consisting of isobutanol, sec-butanol and t-butanol, amyl alcohol, hexyl alcohol, and octyl alcohol.
17. The monoisocyanate compound (e) described in 10 above is (meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono to diisocyanate compound. (Meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) A small amount selected from the group consisting of monoadducts of acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, and allyloxyethanol. Wherein a Kutomo one compound thermosetting resin composition according to any one of 10 to 16.
18. The thermosetting resin composition according to any one of 10 to 17, wherein the carboxyl group-containing urethane resin has a number average molecular weight of 1000 to 100,000 and an acid value of 5 to 120 mg-KOH / g.
19. 19. The thermosetting resin composition according to 18, wherein the carboxyl group-containing urethane resin has a number average molecular weight of 3000 to 50000 and an acid value of 10 to 70 mg-KOH / g.
20. The thermosetting resin composition according to any one of 10 to 19, wherein a polyepoxy compound is contained as a curing agent with respect to the carboxyl group-containing urethane resin.
21. 21. The thermosetting resin composition as described in 20 above, wherein the curing agent is bisphenol-A, bisphenol-F and / or a hydrogenated epoxy resin thereof.
22. 22. The thermosetting resin composition as described in 21 above, wherein the curing agent is an alicyclic epoxy compound.
23. (B) Inorganic and / or organic fine particles described in 1 above are silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, glass powder, quartz powder as inorganic fine particles, and epoxy resin powder as organic fine particles. , At least one compound selected from the group consisting of melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, and silicone powder at a ratio of 5 to 40% by mass with respect to the entire thermosetting resin composition. The thermosetting resin composition according to any one of 1 to 22 above.
24. The thermosetting resin composition according to any one of 1 to 23, wherein (C) the fluorine-containing polyether according to 1 is a copolymer of an epoxy compound, an oxetane compound and / or a tetrahydrofuran derivative and a fluorooxetane. .
25. The overcoat agent for flexible substrates containing the thermosetting resin composition in any one of said 1-24.
26. 26. A surface protective film for a flexible substrate comprising the overcoat agent as described in 25 above.
27. The ink for permanent insulation protective films containing the thermosetting resin composition in any one of said 1-26.
28. A cured product obtained by curing the ink for a permanent insulating protective film as described in 27 above.
29. 29. An electronic component comprising the cured product as described in 28 above.

  The thermosetting resin composition of the present invention is excellent in defoaming properties and leveling properties during printing, without using a silicone-based antifoaming agent, adhesion to the substrate, low warpage, flexibility, resistance to resistance. A paste-like thermosetting resin composition, an overcoat agent and a surface protective film excellent in plating property, solder heat resistance, and long-term reliability at high temperature and high humidity are provided.

Hereinafter, the thermosetting resin composition and the protective film forming material of the present invention will be described in more detail.
The present invention is a paste-like thermosetting resin composition containing the following components (A), (B) and (C).
(A) thermosetting resin,
(B) inorganic fine particles and / or organic fine particles, and (C) fluorine-containing polyether.

  The thermosetting resin composition of the present invention comprises the thermosetting resin (A), a solvent as necessary, inorganic and / or organic fine particles (B) as a filler, and a fluorine-containing polyether (S) as a surfactant. C), an antifoaming agent, a curing accelerator and the like are further blended and kneaded, and a film forming material is preferably prepared by adding a curing agent thereto. The protective film can be obtained by using a curing method such as drying and heating after applying it by screen printing or the like.

(A) Thermosetting resin As the thermosetting resin (A) that can be used in the present invention, any thermosetting resin that can be generally used for a resin composition for a protective film can be used. Examples include epoxy resins, elastomer-modified products of epoxy resins, urethane resins, elastomer-modified products of urethane resins, polyimide resins and elastomer-modified products of polyimide resins, and acrylic acid-modified products thereof. It can also be used.

As the epoxy resin, a combination of an epoxy resin and a curing agent is common.
Typical epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin or alicyclic epoxy resin in one molecule. And an epoxy resin having two or more epoxy groups.
Examples of the curing agent include amines, imidazoles, acid anhydrides, phenols, quaternary ammonium salts, methylol group-containing compounds, and the like.

  Examples of the urethane resin include polyurethane resins based on polybutadiene diol as disclosed in, for example, JP-A Nos. 2000-186248 and 11-071551.

  Examples of polyimide resins include polyamideimide resins such as those disclosed in JP-A Nos. 2001-30295, 2004-137370, and 2004-211055, and JP-A-2004-169042. Examples thereof include polyimide siloxane resins as disclosed in Japanese Unexamined Patent Application Publication No. 2004-211064.

  Further, when the following specific carboxyl group-containing urethane is used as the thermosetting resin, a resin composition for a protective film having a good balance between electrical properties and flexibility can be obtained particularly after curing.

Such a carboxyl group-containing urethane is synthesized by reacting the following raw materials in a charged molar ratio described later.
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
Further, as required (d) a monohydroxy compound, and (e) a monoisocyanate compound.

(A) Polyisocyanate compound Specifically, the polyisocyanate compound (a) is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3. -Trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate 1,4-cyclohexane diisocyanate, 2,2′-diethyl ether diisocyanate, diphenylmethane-4,4′-diisocyanate, (o, m, or p) -xylene diisocyanate, methylene bi (4-cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4, Examples of the diisocyanate include 4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, and norbornane diisocyanate. These can be used alone or in combination of two or more.

  The above-mentioned polyisocyanate compound (a) usually has two isocyanate groups per molecule. However, if the polyurethane of the present invention does not gel, there are three or more isocyanate groups such as triphenylmethane triisocyanate. A small amount of polyisocyanate can also be used. Specifically, for example, it can be used at 5 mol% or less of the isocyanate compound to be used.

  Among these polyisocyanate compounds, particularly when an alicyclic compound having 6 to 30 carbon atoms excluding an isocyanate group (NCO group) is used, the cured product of the present invention has the most excellent high temperature and high humidity. Express long-term insulation reliability performance.

  These alicyclic compounds are desirably contained in an amount of 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more based on the total amount (100 mol%) of the polyisocyanate compound (a). Specific examples of these alicyclic compounds include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate and cyclohexane-1,4-dimethylene diisocyanate. Can be mentioned.

(B) Polyol compound As for the polyol compound (b), the number of carbon atoms in the constituent components which does not contain oxygen except in the polycarbonate polyol, polyether polyol, polyester polyol, polylactone polyol, polybutadiene polyol, hydroxylated polyhydroxyl at both ends, and hydroxyl groups. One or more selected from polyol compounds having a value of 18 to 72 as raw materials.

（式中、Ｒは対応するジオールから水酸基を除いたものであり、ｎは繰返し単位数である。） The polycarbonate polyol can be obtained by reacting a diol having 4 to 18 carbon atoms with a carbonate or phosgene. Specifically, it is represented by the following structural formula.

(In the formula, R is a group obtained by removing the hydroxyl group from the corresponding diol, and n is the number of repeating units.)

  Specific examples of the diol as a raw material include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,8-octanediol. 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, etc. Can be used.

  As the polycarbonate polyol, polycarbonate diol is particularly preferably used. The polycarbonate diol may be a polycarbonate diol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate diol), and the use of the copolymerized polycarbonate diol is advantageous from the viewpoint of preventing crystallization of the produced polyurethane. There are many cases. In view of solubility in a solvent, it is preferable to partially use a polycarbonate diol having a side chain substituent.

（式中のＲは対応するジオールから水酸基を除いたものであり、ｎは繰返し単位数である。）
具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリ−１，２−ブチレングリコール、ポリテトラメチレングリコール、ポリ−３−メチルテトラメチレングリコール等が挙げられる。また、相溶性、疎水性を向上する目的でこれらの共重合体も用いることができる。 As the polyether polyol, those obtained by dehydration condensation of diols having 2 to 12 carbon atoms or ring-opening polymerization of oxirane compounds, oxetane compounds or tetrahydrofuran compounds having 2 to 12 carbon atoms are used. Specifically, it is represented by the following structural formula.

(In the formula, R is a group obtained by removing the hydroxyl group from the corresponding diol, and n is the number of repeating units.)
Specific examples include polyethylene glycol, polypropylene glycol, poly-1,2-butylene glycol, polytetramethylene glycol, and poly-3-methyltetramethylene glycol. These copolymers can also be used for the purpose of improving compatibility and hydrophobicity.

（式中、Ｒ¹は対応するジオールから水酸基を除いたものであり、Ｒ²は対応するジカルボン酸からカルボキシル基を除いたものであり、ｎは繰返し単位数である。） As the polyester polyol, those obtained by dehydrating and condensing the following dicarboxylic acid and diol, or by subjecting an esterified product of a lower alcohol of dicarboxylic acid and a diol to a transesterification reaction are used. Specifically, it is represented by the following structural formula.

(In the formula, R ¹ is obtained by removing the hydroxyl group from the corresponding diol, R ² is obtained by removing the carboxyl group from the corresponding dicarboxylic acid, and n is the number of repeating units.)

  Specific diols used for the synthesis of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol or 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol , 1,3-xylylene glycol, 1,4-xylylene glycol, diethyl Glycol, triethylene glycol, dipropylene glycol, and the like.

  Dicarboxylic acids used for the synthesis of polyester polyols include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, methyl Tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2 , 6-naphthalenedicarboxylic acid.

（式中、Ｒ¹は対応するヒドロキシアルカン酸から水酸基とカルボキシル基を除いたものであり、Ｒ²は対応するジオールから水酸基を除いたものであり、ｎは繰返し単位数である。）
具体的には、３−ヒドロキシブタン酸、４−ヒドロキシペンタン酸、５−ヒドロキシヘキサン酸（ε−カプロラクトン）等が挙げられる。 The polylactone polyol is obtained by ring-opening polymerization of a diol and a lactone compound or a condensation reaction of a diol and a hydroxyalkanoic acid, and is represented by the following structural formula.

(In the formula, R ¹ is a group obtained by removing a hydroxyl group and a carboxyl group from a corresponding hydroxyalkanoic acid, R ² is a group obtained by removing a hydroxyl group from a corresponding diol, and n is the number of repeating units.)
Specific examples include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, and 5-hydroxyhexanoic acid (ε-caprolactone).

As the polybutadiene polyol, those obtained by polymerizing butadiene or isoprene by anionic polymerization and introducing hydroxyl groups at both ends by terminal treatment, and those obtained by reducing these double bonds with hydrogen can also be used.
Specifically, a hydroxylated polybutadiene mainly having 1,4-repeating units (for example, Poly bd R-45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.)), a hydroxylated hydrogenated polybutadiene (for example, polytail) H, polytail HA (manufactured by Mitsubishi Chemical Corporation)), hydroxylated polybutadiene mainly having 1,2-repeating units (for example, G-1000, G-2000, G-3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxyl group Hydrogenated polybutadiene (for example, GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxyl-terminated polyisoprene (for example, Poly IP (manufactured by Idemitsu Kosan Co., Ltd.)), hydrogenated polyisoprene ( For example, Epaul (made by Idemitsu Kosan Co., Ltd.) is mentioned.

（式中、Ｒ¹は炭素数２〜５０の脂肪族炭化水素基又は芳香族炭化水素基を表し、エーテル基を含んでいてもよく；Ｒ²及びＲ³は、それぞれ独立して炭素数１〜１２の脂肪族炭化水素基又は芳香族炭化水素基を表し、ｎは繰返し単位数である。）
市販品としては、例えば信越化学工業株式会社製「X-22-160AS、KF6001、KF6002、KF-6003」などが挙げられる。 Both terminal hydroxylated polysilicones are represented by the following structural formula.

(In the formula, R ¹ represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 2 to 50 carbon atoms, and may contain an ether group; R ² and R ³ each independently represent 1 carbon atom. Represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group of ˜12, and n is the number of repeating units.)
Examples of commercially available products include “X-22-160AS, KF6001, KF6002, KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The polyol compound containing no oxygen other than the hydroxyl group and having 18 to 72 carbon atoms as a constituent component is specifically a diol compound having a skeleton obtained by hydrogenating dimer acid. Examples of commercially available products include cognis. Examples include “Sovermol908” manufactured by the company.

  Further, as the other polyol compound (b), a diol having a molecular weight of 300 or less can be used as long as the physical properties are not impaired. Specific examples of such low molecular weight diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol 1,3-xylylene glycol, 1,4-xylylene glycol, diethylene glycol, tri Ji glycol, and dipropylene glycol.

(C) Dihydroxy compound containing a carboxyl group Specific examples of the dihydroxy compound (c) containing a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bis. Examples thereof include hydroxyethyl glycine and N, N-bishydroxyethylalanine. Among them, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferable from the viewpoint of solubility in a solvent. These dihydroxy compounds containing a carboxyl group can be used singly or in combination of two or more.

  The carboxyl group-containing polyurethane of the present invention can be synthesized only from the above three components (a), (b), and (c). Further, the purpose of imparting radical and cationic polymerizability to this polyurethane Alternatively, the monohydroxy compound (d) and / or the monoisocyanate compound (e) can be reacted for the purpose of eliminating the influence of the isocyanate residue and hydroxyl group at the end of the polyurethane.

(D) Monohydroxy compound The monohydroxy compound (d) used for the purpose of imparting radical polymerizability or cationic polymerizability is a compound having a radical polymerizable double bond or a compound having a cationic polymerizable functional group. Well, examples of the former compound having a radical polymerizable double bond include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, Caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) a Relate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxy ethanol, 1,4-butanediol monovinyl ether, cyclohexanedimethanol monovinyl ether. Examples of the latter compound having a cationic polymerizable functional group include compounds having a hydroxyl group and a carboxyl group. Specifically, glycolic acid, hydroxypivalic acid, lactic acid, malic acid, citric acid, 2-hydroxyethylpropionic acid. And hydroxyisobutyric acid.

  These monohydroxy compounds can be used alone or in combination of two or more. Among these compounds, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, glycolic acid and hydroxypivalic acid are preferable, and 2-hydroxyethyl (meth) ) Acrylate is more preferred.

  As the monohydroxy compound (d) used for the purpose of eliminating the influence of the isocyanate residue at the terminal of the polyurethane, in addition to the above monohydroxy compound, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, Low molecular weight alcohols such as sec-butanol, t-butanol, amyl alcohol, hexyl alcohol, and octyl alcohol can also be used.

(E) Monoisocyanate compound Monoisocyanate compound (e) has a radical double bond, (meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate for diisocyanate compound, hydroxypropyl (meth) Acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol Allyloxy mono adduct of ethanol.

  Examples of the monoisocyanate hydroxy compound used for the purpose of eliminating the influence of the terminal hydroxyl residue include phenyl isocyanate, hexyl isocyanate, and dodecyl isocyanate.

  The carboxyl group-containing polyurethane of the present invention preferably has a number average molecular weight of 1,000 to 100,000, more preferably 3,000 to 50,000. Here, the molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC). If the molecular weight is less than 1000, the elongation, flexibility, and strength of the cured film may be impaired. If the molecular weight exceeds 100,000, the solubility in a solvent is lowered and the viscosity becomes too high even if dissolved. , Restrictions on usage may increase.

In this specification, unless otherwise specified, the measurement conditions of gel permeation chromatography (GPC) are as follows.
Apparatus name: JASCO Corporation HPLC unit HSS-2000,
Column: Shodex column LF-804,
Mobile phase: tetrahydrofuran,
Flow rate: 1.0 mL / min,
Detector: RI-2031Plus manufactured by JASCO Corporation,
Temperature: 40.0 ° C
Sample volume: 100 μl of sample loop,
Sample concentration: Adjust to around 0.1 wt%.

  The acid value of the carboxyl group-containing polyurethane of the present invention is preferably 5 to 120 mg-KOH / g, and more preferably 10 to 70 mg-KOH / g. When an acid value is less than 5 mg-KOH / g, the reactivity with other curable resins, such as an epoxy resin, may fall and heat resistance may be impaired. Moreover, when it exceeds 120 mg-KOH / g, the cured film may be too hard and brittle.

In addition, the acid value of the resin in this specification was measured by the following method.
About 0.2 g of a sample was precisely weighed with a precision balance in a 100 ml Erlenmeyer flask, and 10 ml of a mixed solvent of ethanol / toluene = 1/2 (mass ratio) was added and dissolved therein. Further, 1 to 3 drops of phenolphthalein ethanol solution is added as an indicator, and the mixture is sufficiently stirred until the sample becomes uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is reached when the indicator is slightly red for 30 seconds. The value obtained from the result using the following calculation formula is defined as the acid value of the resin.
Acid value (mg-KOH / g) = [B × f × 5.611] / S
B: Amount of 0.1N potassium hydroxide-ethanol solution used (ml),
f: a factor of 0.1N potassium hydroxide-ethanol solution, in this case 1,
S: Amount of sample collected (g).

  The carboxyl group-containing polyurethane of the present invention is prepared by using a suitable organic solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate, and using polyisocyanate (a), polycarbonate diol (b), dihydroxy. It can be synthesized by reacting the compound (c) and, if necessary, the monohydroxy compound (d) and the monoisocyanate compound (e), but a cured film is finally produced by reacting without a catalyst. Therefore, the physical property value is improved when actually used, which is preferable.

  As the organic solvent, a solvent having low reactivity with isocyanate can be used, and a solvent having no basic functional group such as amine and having a boiling point of 110 ° C. or higher, preferably 200 ° C. or higher is preferable. Examples of such solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether. Acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone γ- butyrolactone, dimethyl sulfoxide, can be mentioned chloroform and methylene chloride.

  In view of the fact that the organic solvent having low solubility of the resulting carboxyl group-containing polyurethane is not preferable, and considering that polyurethane is used as a raw material for ink in electronic material applications, among these, in particular, propylene glycol methyl ether acetate, propylene Glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, γ-butyrolactone and the like are preferable.

  Although there is no restriction | limiting in particular about the order which charges a raw material, Usually, after charging polycarbonate diol (b) and a dihydroxy compound (c) first and making it melt | dissolve in a solvent, 20-150 degreeC, More preferably, it is 60-120. The diisocyanate compound (a) is added dropwise at 0 ° C., and then reacted at 30 to 160 ° C., more preferably at 50 to 130 ° C.

  The molar ratio of the raw materials is adjusted according to the molecular weight and acid value of the polyurethane to be synthesized. When the monohydroxy compound (d) is introduced into the polyurethane, the polycarbonate is used so that the end of the polyurethane molecule is an isocyanate group. It is necessary to use the diisocyanate compound (a) in the same amount or in excess of the diol (b) and the dihydroxy compound (c) (so that the isocyanate groups are in excess of the total of hydroxyl groups).

Specifically, the charged molar ratio of diisocyanate compound (a) :( polycarbonate diol (b) + dihydroxy compound (c)) is preferably 0.5 to 1.5: 1. 8 to 1.2: 1 is more preferred.
Moreover, it is preferable that polycarbonate diol (b): dihydroxy compound (c) is 1: 0.1-30, and 1: 0.3-10 is still more preferable.

  In the case of using the monohydroxy compound (d), the number of moles of the diisocyanate compound (a) is made equal to or excessive from the number of moles of (polycarbonate diol (b) + dihydroxy compound (c)), and the monohydroxy compound (d ) Is used in an amount of 0.5 to 1.5 times mol, preferably 0.8 to 1.2 times mol, based on the excess number of moles of NCO groups.

  When the monoisocyanate compound (e) is used, the number of moles of (polycarbonate diol (b) + dihydroxy compound (c)) is made larger than the number of moles of the diisocyanate compound (a), and the number of moles of hydroxyl groups is excessive. , 0.5 to 1.5 times the molar amount, preferably 0.8 to 1.2 times the molar amount.

  In order to introduce the monohydroxy compound (d) into the polyurethane, when the reaction between the polycarbonate diol (b) and the dihydroxy compound (c) and the diisocyanate (a) is almost completed, both ends of the polyurethane are introduced. In order to react the remaining isocyanate group with the monohydroxy compound (d), the monohydroxy compound (d) is dropped into the polyurethane solution at 20 to 150 ° C., more preferably at 70 to 120 ° C., and then Hold at the same temperature to complete the reaction.

  In order to introduce the monoisocyanate compound (e) into the polyurethane, at the time when the reaction between the polycarbonate diol (b) and the dihydroxy compound (c) and the diisocyanate (a) is almost completed, both ends of the polyurethane are introduced. In order to react the remaining hydroxyl group with the monoisocyanate compound (e), the monoisocyanate compound (e) is dropped into the polyurethane solution at 20 to 150 ° C., more preferably at 50 to 120 ° C., and then the same. Hold at temperature to complete reaction.

(B) Inorganic or organic fine particles (filler)
Known inorganic or organic fine particles can be used. The blending ratio varies depending on the thermosetting resin to be used, but when it is added, it is preferably in the range of 10 to 40% by mass with respect to the entire resin composition.
Examples of organic fillers include epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, and silicone powder.Inorganic fillers include silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, Examples thereof include glass powder and quartz powder.

(C) Fluorine-containing polyether (surfactant)
The thermosetting resin composition of the present invention is a polymer containing any one of the fluorinated alkyl polyoxetane structures represented by the following general formula (1) or (2), or a monomer containing the fluorinated alkyl polyoxetane structures. And a copolymer comprising a monomer containing an oxygen atom having 2 to 6 carbon atoms as a surfactant.

（式中、ｍは１〜１００の整数を表し、ｎは１〜６の整数を表し、Ｒ¹は水素原子又は炭素数１〜６のアルキル基を表し、Ｒ²及びＲ³はそれぞれ独立して、炭素数１〜２０の直鎖又は分岐鎖のアルキル基を表す。ただし、該アルキル基中の水素原子の少なくとも５０％がフッ素原子で置換され、残りは水素原子、もしくはヨウ素原子、塩素原子、又は臭素原子で置換されている。）

(In the formula, m represents an integer of 1 to 100, n represents an integer of 1 to 6, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are each independently selected. Represents a linear or branched alkyl group having 1 to 20 carbon atoms, provided that at least 50% of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the rest are hydrogen atoms, iodine atoms, chlorine atoms Or substituted with a bromine atom.)

Of the hydrogen atoms in the alkyl group represented by R ² or R ³ in the formula, at least 50% or more, more preferably 75% or more, and most preferably 95% or more are substituted with fluorine atoms. Is desirable. If the substitution amount of fluorine atoms is small, desired leveling properties and antifoaming properties cannot be obtained.

In addition, if the alkyl group represented by R ² or R ³ is too long, the desired defoaming effect may not be obtained, so the carbon number of the alkyl group represented by R ² or R ³ is 20 Hereinafter, it is preferably 7 or less, more preferably 3 or less. For the same reason, n in the formula is also 6 or less, preferably 3 or less, more preferably 1 is desirable.

  Moreover, as m in a formula, 2-100, More preferably, 2-30 are preferable. If the molecular weight of the polyether is small, not only the performance as a surfactant may be exhibited, but bleeding may occur, and even if the molecular weight is too large, the performance of the surfactant will not be manifested, and bulky foreign matter Will be the cause.

  Further, the number average molecular weight of the fluorine-containing polyether (C) is preferably about 300 to about 10,000, and more preferably 1000 to 8000.

[Polymer containing fluorinated alkylpolyoxetane structure]
As the polymer containing the fluorinated alkylpolyoxetane structure represented by the general formula (1) or (2), a commercially available product may be used, or the polyether compound may be synthesized by a known method.
As an example of a commercially available product, PolyFOX PF656 (manufactured by Omninova Solutions, Inc.) (a compound in which m = 6, n = 1, R ¹ = CH ₃ , R ² = C ₂ F ₅ in the general formula (1)) ), PolyFOX PF636 (manufactured by the same company) (a compound in which m = 6, n = 1, R ¹ = R ² = CH ₃ in the general formula (1)), PolyFOX PF6320 (made by the same company) (in the general formula (1) , M = 20, n = 1, R ¹ = R ² = CH ₃ compound) and PolyFOX PF6520 (manufactured by the same company) (in general formula (1), m = 20, n = 1, R ¹ = CH ₃ , R ² = C ₂ F ₅ )) and the like.

又は

（式中、ｎ及びＲ¹〜Ｒ³の符号の意味は前記に示した通り。）で表される環状エーテルを、ルイス触媒、例えば、三フッ化ホウ素錯体（例えば、三フッ化ホウ素エテレート、三フッ化ホウ素テトラヒドロフラン（ＴＨＦ））、ホスホラスペンタフルオライド、アンチモンペンタフルオライド、塩化亜鉛、臭化アルミニウムなどの存在下、不活性溶媒の存在下で重合させることにより得ることもできる。不活性溶媒は、通常、１〜約６個の炭素原子を含む炭化水素又はハロゲン化溶媒であり、具体例としては塩化メチレン、四塩化炭素、トリクロロエチレン、クロロベンゼン、ジクロロエタンなどが挙げられる（例えば、特表２００４−５３５４８５号公報参照）。 For example,

Or

(Wherein the meanings of n and the symbols R ^{1 to} R ³ are as described above) are converted to Lewis catalysts such as boron trifluoride complexes (for example, boron trifluoride etherate, Boron trifluoride tetrahydrofuran (THF)), phosphorous pentafluoride, antimony pentafluoride, zinc chloride, aluminum bromide and the like, and polymerization in the presence of an inert solvent can also be used. The inert solvent is usually a hydrocarbon or halogenated solvent containing 1 to about 6 carbon atoms, and specific examples include methylene chloride, carbon tetrachloride, trichloroethylene, chlorobenzene, dichloroethane, etc. (See Table 2004-535485).

  The polymer containing a fluorinated alkylpolyoxetane structure represented by the general formula (1) or (2) may be a homopolymer consisting of any one of repeating units or a copolymer in which these are mixed. Moreover, the copolymer which consists of a monomer containing either of these repeating units and a C2-C6 oxygen atom may be sufficient. For example, a copolymer of an epoxy compound, an oxetane compound and / or a tetrahydrofuran derivative and fluorooxetane can be given.

  Examples of the monomer containing an oxygen atom having 2 to 6 carbon atoms include mono- or polyhydroxyl alcohol and cyclic ether containing 2 to 6 carbon atoms in the molecule. Specific examples of mono- or polyhydroxyl alcohol include ethylene glycol, butane-1,4-diol, propylene glycol, isobutane-1,3-diol, pentane-1,5-diol, pentaerythritol, trimethylolpropane, etc. Examples include ethanol. These monomers may be contained in the copolymer as oligomers or polymers, and examples of such oligomers or polymers include diethylene glycol, polyethylene glycol, polypropylene glycol and the like. Examples of cyclic ethers include epoxy compounds, oxetane compounds, and tetrahydrofuran derivatives. These may have a substituent such as alkyl, fluorine and other halogens on the carbon atoms constituting the ring.

[Combination ratio]
The thermosetting resin composition used in the present invention comprises a component (A) thermosetting resin, component (B) inorganic fine particles and / or organic fine particles and component (C) fluorine-containing polyether. (A) Thermosetting resin 20-90 mass% with respect to the whole quantity,
(B) 10-80% by mass of inorganic fine particles and / or organic fine particles,
(C) fluorine-containing polyether 0.1 to 5% by mass,
Preferably (A) 40-90 mass% of thermosetting resin,
(B) 10 to 60% by mass of inorganic fine particles and / or organic fine particles,
(C) fluorine-containing polyether 0.1 to 5% by mass,
Especially preferably (A) 60-85 mass% of thermosetting resin,
(B) 10 to 40% by mass of inorganic fine particles and / or organic fine particles,
(C) fluorine-containing polyether 0.1 to 5% by mass,
It is characterized by being blended at a ratio of

Moreover, the thermosetting resin composition of the present invention can also be used for various applications other than overcoat agents for flexible substrates, for example, when used for heat dissipation parts,
(A) 20-50 mass% of thermosetting resin,
(B) 50-80% by mass of inorganic fine particles and / or organic fine particles,
(C) fluorine-containing polyether 0.1 to 5% by mass,
It is preferable to mix | blend in the ratio.

[Curing agent]
As the curing agent, one that cures the carboxyl group-containing polyurethane is selected, and among them, an epoxy resin is preferable.
Epoxy resins include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, phenol novolak type epoxy resin. Resin, cresol novolac type epoxy resin, alicyclic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, Examples include epoxy compounds having two or more epoxy groups in one molecule such as dicyclopentadiene phenolic epoxy resin, silicone-modified epoxy resin, and ε-caprolactone-modified epoxy resin. That. Of these, alicyclic epoxy compounds are particularly preferred.

Further, in order to impart flame retardancy, a material in which atoms such as halogen such as chlorine and bromine and phosphorus are introduced into the structure may be used. Furthermore, bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylenoyl ethane resin, and the like may be used.
The epoxy resin preferably contains an epoxy resin having two or more epoxy groups. However, you may contain the epoxy resin which has one epoxy group.

[solvent]
It is preferable that the thermosetting resin composition of the present invention contains a solvent. More preferably, it is preferable to take a form in which a thermosetting resin is dissolved in a solvent, and it is particularly preferable that the thermosetting resin is dissolved in the solvent used for the synthesis.
After synthesis, when trying to obtain a thermosetting resin composition as a solid, it is difficult to disperse the thermosetting resin without using a solvent, and the step of dissolving the synthesized solid with a solvent Is necessary and economically undesirable.
The solvent is not particularly limited as long as the thermosetting resin can be dissolved, but the boiling point is preferably 30 to 400 ° C, more preferably 110 to 300 ° C.

  Specific types of solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol. Methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N , N-dimethylformamide, N, N-dimethylacetoa De, N- methylpyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, and the like can be exemplified chloroform and methylene chloride.

  As a usage-amount of a solvent, the carboxyl group-containing polyurethane density | concentration (solid content density | concentration) in this thermosetting resin composition becomes like this. Preferably it is 10-90 mass%, More preferably, the quantity used as 30-80 mass% is added.

[Defoamer]
As the antifoaming agent, other non-silicone antifoaming agents can be used to supplement the fluorine-based surfactant. These may be used in combination of several types as well as one type, and the amount and ratio of mixing are not particularly limited, and can be changed as appropriate in consideration of bubble entrainment properties and bubble removal properties during screen printing. Examples of such non-silicone antifoaming agents include BYK-A500 (manufactured by Big Chemie Japan Co., Ltd .: trade name), BYK-A501 (manufactured by BYK Chemie Japan Co., Ltd .: trade name), and BYK-A515 (stock of Big Chemie Japan). Company: product name), BYK-A555 (Bic Chemie Japan Co., Ltd. product name), etc. are preferably used.

[Curing accelerator]
Examples of the curing accelerator include imidazole derivatives (for example, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, manufactured by Shikoku Kasei Kogyo Co., Ltd. 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, etc.); Polyamines such as phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide; these organic acid salts and / or epoxy adducts; Boron halide amine complexes; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol, etc. Amines; Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak; organic phosphines such as tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine; tri-n-butyl Phosphonium salts such as ru (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the polybasic acid anhydrides; diphenyliodonium tetrafluoroboro Cation, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Ciba Geigy, Irgacure 261, Asahi Denka Co., Ltd., Optoma-SP-170, etc. Polymerization catalyst; styrene-maleic anhydride resin; equimolar reaction product of phenyl isocyanate and dimethylamine, tolylene diisocyanate, isophorone diisocyanate, etc. And known curing agents or curing accelerators such as an equimolar reaction product of organic polyisocyanate and dimethylamine.

[Other additives]
The thermosetting resin composition further includes various known additives, such as fiber reinforcing materials such as glass fiber, carbon fiber, boron nitride fiber, titanium oxide, zinc oxide, carbon black, iron black, organic pigment, Colorants such as organic dyes, antioxidants such as hindered phenol compounds, phosphorus compounds and hindered amine compounds, UV absorbers such as benzotriazole compounds and benzophenone compounds can be blended.

Moreover, a viscosity modifier, a flame retardant, an antibacterial agent, an antifungal agent, an anti-aging agent, an antistatic agent, a plasticizer, a lubricant, a foaming agent, and the like can be added and mixed according to the application.
As the kneading method, dissolution or dispersion is performed using a mixer such as a disper, a kneader, a three-roll mill, a bead mill, or a homogenizer.
The cured product of the present invention thus obtained has good antifoaming and leveling properties without using a silicone-based antifoaming agent, and has low warpage, flexibility, plating resistance, solder heat resistance, electrical Excellent long-term insulation reliability.

  The present invention also provides an overcoat agent for a flexible substrate containing the above-described thermosetting resin composition, a surface protective film comprising the overcoat agent, a permanent insulating protective film ink, and a permanent insulating protective film ink. A cured product obtained by curing, and an electronic component including the cured product are included.

  The present invention will be described below with reference to synthesis examples and examples, but the present invention is not limited to these examples.

Synthesis example 1:
In a reaction vessel equipped with a stirrer, thermometer and condenser,
(B) C-1015N as a polyol compound (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, molecular weight 964) 660.6 g (0.69 mol), G-1000 (manufactured by Nippon Soda Co., Ltd., both terminal hydroxylated 1,2-polybutadiene, molecular weight 1548) 73.39 g, (0.05 mol) (c) 2 as a dihydroxyl compound having a carboxyl group , 2-dimethylolbutanoic acid (Nippon Kasei Co., Ltd.) 138.4 g (0.93 mol), diethylene glycol ethyl ether acetate (Daicel Chemical Industries, Ltd.) 1303 g as a solvent, and 2,2-dimethylol at 90 ° C. Butanoic acid was dissolved. The temperature of the reaction liquid was lowered to 70 ° C., and 437.3 g (1.67 mol) of Desmodur-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate over 30 minutes using a dropping funnel. After completion of dropping, the reaction was carried out at 80 ° C. for 1 hour, 100 ° C. for 1 hour, and 120 ° C. for 2 hours. After confirming that the isocyanate had almost disappeared, (d) isobutanol (Wako Pure Chemical Industries, Ltd.) 5 g (0.07 mol) was added dropwise and further reacted at 120 ° C. for 1.5 hours.
The obtained carboxyl group-containing polyurethane had a number average molecular weight of 13,800 and an acid value of solid content of 40.2 mg-KOH / g.

Synthesis example 2:
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 1172 g (0.76 mol) of G-1000 (same as above) as a (b) polyol compound, and (c) 2,2-as a dihydroxyl compound having a carboxyl group. 172 g (1.16 mol) of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 1744 g of diethylene glycol ethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.) as the solvent were charged, and all raw materials were dissolved at 90 ° C. The temperature of the reaction solution was lowered to 70 ° C., and 504 g (1.92 mol) of Desmodur-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate over 30 minutes using a dropping funnel. After completion of dropping, the reaction was carried out at 80 ° C. for 3 hours, 90 ° C. for 3 hours, and 100 ° C. for 3 hours. After confirming that the isocyanate had almost disappeared, (d) isobutanol (Wako Pure Chemical Industries, Ltd.) 4.4 g (0.06 mol) was added dropwise, and the reaction was further carried out at 100 ° C. for 1.5 hours.
The obtained carboxyl group-containing polyurethane had a number average molecular weight of 7,800 and an acid value of solid content of 35.0 mg-KOH / g.

Synthesis Example 3:
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, (b) C-1065N (produced by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8 as a polyol compound) -Octanediol = 65:35, molecular weight 991) 70.7 g (0.07 mol), (c) 13.5 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as a dihydroxyl compound having a carboxyl group 0.09 mol), and 128.9 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was charged as a solvent, and all raw materials were dissolved at 90 ° C. The temperature of the reaction solution was lowered to 70 ° C., and 42.4 g (0.16 mol) of Desmodur-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate over 30 minutes using a dropping funnel. After completion of the dropping, the reaction was carried out at 80 ° C. for 1 hour, 90 ° C. for 1 hour, and 100 ° C. for 2 hours. After confirming that the isocyanate had almost disappeared, (d) isobutanol (Wako Pure Chemical Industries) as the monohydroxy compound 1.46 g (0.015 mol) was added dropwise and further reacted at 105 ° C. for 1.5 hours.
The obtained carboxyl group-containing polyurethane had a number average molecular weight of 6800 and an acid value of solid content of 39.9 mg-KOH / g.

Synthesis Example 4:
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, (b) C-2015N (polycarbonate diol, polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8 as polycarbonate diol) -Octanediol = 15: 85, molecular weight 1945) 305.0 g (0.16 mol), (c) 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 52.4 g as a dihydroxyl compound having a carboxyl group ( 0.35 mol) and 494.9 g of diethylene glycol ethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.) as a solvent were charged, and all raw materials were dissolved at 90 ° C. The temperature of the reaction solution was lowered to 70 ° C., and 133.8 g (0.51 mol) of Desmodur-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate over 30 minutes using a dropping funnel. After completion of the dropwise addition, the reaction was carried out at 80 ° C. for 1 hour, 90 ° C. for 1 hour, and 100 ° C. for 1.5 hours. After confirming that the isocyanate had almost disappeared, (d) 3.92 g (0.05 mol) (manufactured by Yakuhin Co., Ltd.) was added dropwise, and the reaction was further carried out at 105 ° C. for 2 hours.
The number average molecular weight of the obtained carboxyl group-containing urethane was 9080, and the solid content acid value was 40.1 mg-KOH / g.

Synthesis Example 5:
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, (b) polycarbonate diol C-1015N (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8 -Octanediol = 15:85, molecular weight 964) 805.4 g (0.84 mol), (c) 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as a dihydroxyl compound having a carboxyl group 104.2 g ( 0.70 mol), 1307 g of diethylene glycol ethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.) as a solvent was charged, and all raw materials were dissolved at 90 ° C. The temperature of the reaction solution was lowered to 70 ° C., and 403.6 g (1.54 mol) of Desmodur-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate over 30 minutes using a dropping funnel. After completion of dropping, the reaction was carried out at 80 ° C. for 1 hour, 100 ° C. for 1 hour, and 120 ° C. for 2 hours. After confirming that the isocyanate had almost disappeared, (d) isobutanol (Wako Pure Chemical Industries, Ltd.) 5.7 g (0.08 mol) was added dropwise, and the reaction was further carried out at 125 ° C. for 1.5 hours.
The obtained carboxyl group-containing polyurethane had a number average molecular weight of 12,100 and an acid value of solid content of 30.1 mg-KOH / g.

Synthesis Example 6:
A reaction vessel equipped with a stirrer, a thermometer, and a condenser was charged with 33 g of trimethylolpropane (OH equivalent = 44.72 g / eq.) And 165 g of ethyl diglycol acetate (manufactured by Daicel Chemical Industries, Ltd.) as a solvent. (A) After dropping 132 g of toluene-2,4-diisocyanate (NCO equivalent = 87.08 g / eq.) As a polyisocyanate, the temperature was gradually raised to 80 ° C., and the reaction was continued at that temperature for 2 hours. Continued. Subsequently, 79.8 g of ethyl diglycol acetate as a solvent and (GI) “GI-1000” as polycarbonate diol (OH-terminated hydrogenated polybutadiene, Mn = about 1500, OH equivalent = 801 g / eq., Solid content = 100 w) %: Manufactured by Nippon Soda Co., Ltd.) A solution in which 139 g was dissolved was added dropwise at 80 ° C. over 1 hour, followed by addition reaction at 80 ° C. for 4 hours. The isocyanate group content of this product was 4.7% (NCO equivalent = 894 g / eq.). Further, while maintaining at 80 ° C., 63.2 g of methyl ethyl ketoxime (molecular weight 87.12) was dropped over 2 hours as a blocking agent, and the reaction was continued for 1 hour. When the disappearance of the NCO peak was confirmed by FT-IR (Fourier transform infrared spectroscopy), the temperature was lowered to obtain an end-block polyurethane resin. Number average molecular weight is 16000, block NCO equivalent (including solvent) = 1013 g / eq. Met.

Synthesis Example 7:
In a 5-liter four-necked flask equipped with a stirrer, a cooling pipe with an oil / water separator, a nitrogen introduction pipe and a thermometer, (b) PLACEL CD-220 (produced by Daicel Chemical Industries, Ltd., 1,6-hexane as polycarbonate diol) Trade name of diol-based polycarbonate diol) 1000.0 g (0.50 mol), (a) 250.27 g (1.00 mol) of 4,4′-diphenylmethane diisocyanate as polyisocyanate, and γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) 833.51 g was charged and the temperature was raised to 140 ° C. The reaction was carried out at 140 ° C. for 5 hours to obtain a bi-terminal diisocyanate oligomer.
Further, 288.20 g (1.50 mol) of trimellitic anhydride, (a) 125.14 g (0.50 mol) of 4,4′-diphenylmethane diisocyanate as polyisocyanate and 1361.14 g of γ-butyrolactone were added to this reaction solution, After the temperature was raised to 160 ° C., the mixture was reacted for 6 hours, and the resulting resin was diluted with γ-butyrolactone to obtain a polyamideimide resin solution having a viscosity of 160 Pa · s and a nonvolatile content of 52% by mass. The number average molecular weight of this resin was 18000.

Synthesis Example 8:
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 58.84 g (0.2 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and triglyme (hereinafter abbreviated as TG) as a solvent. In some cases, 120 g was charged and stirred at 180 ° C. in a nitrogen atmosphere. α, ω-bis (3-aminopropyl) polydimethylsiloxane (NH ₂ equivalent = 455 g / eq.) 154.7 g (0.17 mol) and TG 70 g were added, and the mixture was heated and stirred at 180 ° C. for 60 minutes. Further, 8.59 g (0.03 mol) of bis (3-carboxy-4-aminophenyl) methane and 23.4 g of TG were added to this reaction solution, and the mixture was heated and stirred at 180 ° C. for 5 hours, followed by filtration. The obtained polyimidesiloxane reaction solution was a solution having a polymer solid concentration of 50% by mass and ηinh (inherent viscosity; natural logarithm of relative viscosity / mass concentration of polymer) of 0.18. The imidization rate was substantially 100%.

Examples 1-9 and Comparative Examples 1-3:
[Evaluation as a thermosetting composition for overcoat]
<Preparation of thermosetting resin composition>
Using the resins of Synthesis Examples 1 to 8, components other than the surfactant and the leveling agent were appropriately blended with the compositions shown in Table 1. An appropriate amount of carbitol acetate as a viscosity modifier was added and mixed for each formulation, and kneaded using three rolls. Thereafter, a surfactant and a leveling agent were added and mixed with a resin mixer to prepare a sample.

[Evaluation of cured product]
The thermosetting resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were applied to a screen plate ST250-30, a printing speed of 100 mm / second, a clearance between the printing plate and a substrate of 2.0 mm, a squeegee altitude of 80 degrees, and a squeegee. Table 1 shows the results of evaluating the adhesion, the silicone component, and the long-term reliability under the following conditions with respect to what was printed and applied to the substrate at an angle of 70 degrees.

[Defoaming]
A 38 μm-thick polyimide film (Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) was used as a base material, and the thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were printed thereon. Then, after 30 seconds, the number of bubbles remaining in the 50 × 50 mm range was counted and evaluated according to the following criteria.
○: Number of bubbles is 2 or less,
X: The number of bubbles is 3 or more.

[Silicone component]
A 38 μm-thick polyimide film (Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) was used as a base material, and the thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were printed thereon. The film was dried at 80 ° C. for 30 minutes and then thermally cured at 150 ° C. for 24 hours. A 1 mm portion from the end face of the printed portion was subjected to elemental analysis with SEM-EDS (scanning electron microscope-energy dispersive X-ray analyzer) and evaluated according to the following criteria.
O: Mass% of Si component is less than 0.1%,
X: Mass% of Si component is 0.1% or more.

[Long-term reliability of electrical insulation]
A commercially available substrate (IPC standard) IPC-C (comb pattern) was used as a base material, and the thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were printed thereon and applied at 80 ° C. For 30 minutes, followed by heat curing at 150 ° C. for 1 hour. The substrate was allowed to stand for 1000 hours by applying a bias voltage of 100 V in an atmosphere of 85 ° C. and 85% relative humidity, and then the electrical insulation was evaluated according to the following criteria.
○: No migration or decrease in insulation resistance,
X: Migration or decrease in insulation resistance value after 1000 hours or less.

[Adhesion]
A 38 μm-thick polyimide film (Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) was used as a base material, and the thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were printed thereon. And dried at 80 ° C. for 30 minutes and then heat cured at 150 ° C. for 1 hour. The cured film surface of the test piece was thermocompression bonded to a 2 mm thick glass plate via an anisotropic conductive film (CP9420IS, manufactured by Sony Chemical). A 90 ° peel test was performed on the test piece thermocompression-bonded using a tensile tester, and the adhesion strength between the cured film and the polyimide film was measured and evaluated according to the following criteria.
○: Adhesion strength is 10 N / cm or more,
Δ: Adhesive strength of 8 N / cm or more and less than 10 N / cm,
X: Adhesion strength is less than 8 N / cm.

The results are summarized in Table 1 below.

As described above, according to the present invention, without using a silicone-based antifoaming agent, it has excellent defoaming properties and leveling properties during printing, adhesion to a substrate, low warpage, flexibility, resistance to resistance. A thermosetting resin composition having excellent plating properties, solder heat resistance, and long-term reliability at high temperature and high humidity can be provided.
Therefore, the thermosetting resin composition of the present invention is an electrically insulating material such as a thermosetting flexible circuit overcoat resin excellent in flexibility, a thermosetting solder resist or an interlayer insulating film excellent in insulating properties. It can be used in fields such as materials, IC and VLSI sealing materials, and laminates.
When the thermosetting resin composition of the present invention is used as an overcoat agent, it can be produced at a lower cost than a conventionally used liquid polyimide material.
Furthermore, the conventional protective film has a problem that low molecular weight cyclic siloxane derived from a silicone compound is generated as an outgas. However, in the present invention, since a silicone-based antifoaming agent is not used, trouble occurs in the mounting process. Without curing, it is possible to provide a resin composition that provides a protective film excellent in the balance between good adhesion after curing, low warpage and long-term reliability of electrical insulation.

Claims (29)

A thermosetting resin composition containing the following components (A), (B) and (C).
(A) thermosetting resin,
(B) inorganic fine particles and / or organic fine particles, and (C) fluorine-containing polyether. Component (A) thermosetting resin, component (B) inorganic fine particles and / or organic fine particles, and component (C) fluorine-containing polyether with respect to the total amount of the thermosetting resin composition (A) thermosetting resin 20-90% by mass,
(B) 10-80% by mass of inorganic fine particles and / or organic fine particles, and (C) 0.1-5% by mass of fluorine-containing polyether,
The thermosetting resin composition of Claim 1 mix | blended in the ratio. Component (A) thermosetting resin, component (B) inorganic fine particles and / or organic fine particles, and component (C) fluorine-containing polyether with respect to the total amount of the thermosetting resin composition (A) thermosetting resin 40-90% by mass,
(B) 10-60 mass% of inorganic fine particles and / or organic fine particles, and (C) 0.1-5 mass% of fluorine-containing polyether,
The thermosetting resin composition of Claim 2 mix | blended in the ratio. (C) The fluorine-containing polyether is represented by the following general formula (1) or (2)

(In the formula, m represents an integer of 1 to 100, n represents an integer of 1 to 6, R ¹ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ each independently represent Represents a linear or branched alkyl group having 1 to 20 carbon atoms, provided that at least 50% of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the rest are hydrogen atoms, iodine atoms, chlorine atoms or bromine. Substituted with atoms.)
A polymer comprising any one of the fluorinated alkylpolyoxetane structures represented by: or a copolymer comprising a monomer comprising the fluorinated alkylpolyoxetane structure and a monomer comprising an oxygen atom having 2 to 6 carbon atoms, The thermosetting resin composition according to any one of claims 1 to 3.   The thermosetting resin composition according to any one of claims 1 to 4, wherein m in the general formulas (1) and (2) in claim 4 represents an integer of 2 to 30. At least 75% of the hydrogen atoms in the linear or branched alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ in the general formulas (1) and (2) in claim 4 are fluorine. The thermosetting resin composition according to any one of claims 1 to 5, which is substituted with an atom. In the general formula in claim 4 (1) and (2), m represents an integer of 2 to 30, n represents an integer of 1 to 3, R ¹ represents a methyl group or an ethyl group, R ² and R ³ represents a linear or branched alkyl group having 1 to 7 carbon atoms, and at least 95% of the hydrogen atoms in the alkyl group are substituted with fluorine. Thermosetting resin composition.   (C) The number average molecular weights of fluorine-containing polyether are 300-10000, The thermosetting resin composition in any one of Claims 1-7.   The group in which the thermosetting resin (A) is composed of an epoxy resin, an elastomer modified product of an epoxy resin, a urethane resin, an elastomer modified product of a urethane resin, a polyimide resin, an elastomer modified product of a polyimide resin, and an acrylic acid modified product thereof. The thermosetting resin composition according to claim 1, comprising at least one resin component selected from: The thermosetting resin composition in any one of Claims 1-9 in which a thermosetting resin (A) contains the carboxyl group-containing urethane resin obtained by making the following raw materials react.
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
Further, as necessary (d) a monohydroxy compound, and (e) a monoisocyanate compound. The charged molar ratio of component (a) diisocyanate compound, component (b) polycarbonate diol, component (c) dihydroxy compound, component (d) monohydroxy compound and component (e) monoisocyanate compound is
(A): ((b) + (c)) = 0.5 to 1.5: 1,
(B) :( c) = 1: 0.1-30,
Further, when (d) is used, ((b) + (c)) ≦ (a), preferably (d) is 0.5 to 1.5 times the molar amount relative to the excess number of moles of NCO groups. age,
When (e) is used, it is (a) <((b) + (c)), and the molar amount is 0.5 to 1.5 times the molar excess of the hydroxyl group. Thermosetting resin composition. The charged molar ratio of component (a) diisocyanate compound, component (b) polycarbonate diol, component (c) dihydroxy compound, component (d) monohydroxy compound and component (e) monoisocyanate compound is
(A): ((b) + (c)) = 0.8 to 1.2: 1,
(B) :( c) = 1: 0.3-10,
Further, when (d) is used, ((b) + (c)) ≦ (a), preferably (d) is 0.8 to 1.2 moles relative to the excess number of moles of NCO groups. Amount and
When (e) is used, it is (a) <((b) + (c)), and the molar amount is 0.8 to 1.2 times the molar excess of the hydroxyl group. Thermosetting resin composition.   The polyisocyanate compound (a) of the carboxyl group-containing urethane resin according to claim 10 is 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate and cyclohexane-1. The thermosetting resin composition according to claim 10, which is at least one compound selected from the group consisting of 1,4-dimethylene diisocyanate.   The polyol compound (b) according to claim 10 is a polycarbonate polyol, a polyether polyol, a polyester polyol, a polylactone polyol, a polybutadiene polyol, a hydroxylated polysilicon at both terminals, and contains no oxygen except in the hydroxyl group, and has a carbon number of the constituent component. The thermosetting resin composition according to any one of claims 10 to 13, which is at least one compound selected from the group consisting of polyol compounds which are 18 to 72.   The thermosetting resin according to any one of claims 10 to 14, wherein the dihydroxy compound (c) having a carboxyl group according to claim 10 is 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid. Composition.   The monohydroxy compound (d) according to claim 10 comprises 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, both are referred to as 2-hydroxyethyl (meth) acrylate) and hydroxypropyl (meth) acrylate. , Hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxyethanol, 1,4-buta Diol monovinyl ether, cyclohexanedimethanol monovinyl ether, glycolic acid, hydroxypivalic acid, lactic acid, malic acid, citric acid, 2-hydroxyethylpropionic acid, hydroxyisobutyric acid or methanol, ethanol, n-propanol, isopropanol, n-butanol, The thermosetting resin composition according to any one of claims 10 to 15, which is at least one compound selected from the group consisting of isobutanol, sec-butanol and t-butanol, amyl alcohol, hexyl alcohol, and octyl alcohol.   The monoisocyanate compound (e) according to claim 10 is (meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol with respect to the diisocyanate compound. Mono (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Selected from the group consisting of monoadducts of acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol and allyloxyethanol The thermosetting resin composition according to any one of claims 10 to 16 which is one compound even without.   The thermosetting resin composition according to any one of claims 10 to 17, wherein the carboxyl group-containing urethane resin has a number average molecular weight of 1000 to 100,000 and an acid value of 5 to 120 mg-KOH / g.   The thermosetting resin composition according to claim 18, wherein the carboxyl group-containing urethane resin has a number average molecular weight of 3000 to 50000 and an acid value of 10 to 70 mg-KOH / g.   The thermosetting resin composition according to any one of claims 10 to 19, wherein a polyepoxy compound is contained as a curing agent with respect to the carboxyl group-containing urethane resin.   The thermosetting resin composition according to claim 20, wherein the curing agent is bisphenol-A, bisphenol-F and / or a hydrogenated epoxy resin thereof.   The thermosetting resin composition according to claim 21, wherein the curing agent is an alicyclic epoxy compound.   (B) The inorganic and / or organic fine particles according to claim 1 are silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, glass powder, quartz powder as the inorganic fine particles, and epoxy resin as the organic fine particles. A ratio of 5 to 40% by mass of at least one compound selected from the group consisting of powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, and silicone powder with respect to the entire thermosetting resin composition The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is blended.   The thermosetting resin according to any one of claims 1 to 23, wherein the fluorine-containing polyether (C) according to claim 1 is a copolymer of an epoxy compound, an oxetane compound and / or a tetrahydrofuran derivative and a fluorooxetane. Composition.   The overcoat agent for flexible substrates containing the thermosetting resin composition in any one of Claims 1-24.   A surface protective film for a flexible substrate comprising the overcoat agent according to claim 25.   27. A permanent insulating protective film ink comprising the thermosetting resin composition according to any one of claims 1 to 26.   A cured product obtained by curing the permanent insulating protective film ink according to claim 27.   An electronic component comprising the cured product according to claim 28.