JPS5837003A - Thermosetting composition - Google Patents
Thermosetting compositionInfo
- Publication number
- JPS5837003A JPS5837003A JP13502781A JP13502781A JPS5837003A JP S5837003 A JPS5837003 A JP S5837003A JP 13502781 A JP13502781 A JP 13502781A JP 13502781 A JP13502781 A JP 13502781A JP S5837003 A JPS5837003 A JP S5837003A
- Authority
- JP
- Japan
- Prior art keywords
- group
- sulfonium salt
- groups
- composition
- curing
- 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.)
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Links
Abstract
Description
【発明の詳細な説明】
本発明は熱硬化性樹脂組成物に関すゐ、詳しくは本発明
はエポキシ樹脂等の陽イオン重合性有機物質を短時間に
重合し、嵐好な硬化物を得るための潜在性に優れた熱硬
化性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and more specifically, the present invention relates to a thermosetting resin composition for polymerizing a cationic polymerizable organic substance such as an epoxy resin in a short period of time to obtain a cured product with excellent properties. The present invention relates to a thermosetting resin composition having excellent latent properties.
エポキシ樹脂呻の陽イオン重合性有機物質のカチオン重
合触媒は現在まで無機酸、ルイス酸。Until now, the cationic polymerization catalyst for cationic polymerizable organic substances used in epoxy resins has been inorganic acids and Lewis acids.
有機酸やある種のアルキル化剤等数多く知られている。Many organic acids and certain alkylating agents are known.
理想的な触媒は常温での貯蔵安定性が良好で、しかも加
熱すゐと短時間、具体的には数分以内に硬化するもので
あるが、現在まで満足のいく硬化触媒は知られておらず
、多くの場合二箪方弐に依るか、あるいは高温で長時間
加熱して硬化しなければならなかった。また潜在性の硬
化触媒としてよく知られているアミン−ＢＰ、錯体（た
とえばモノエチルアミン−ＢＦ、 ）は加熱によシ硬化
を開始するが、十分の物性を有すゐ硬化物を得るために
は高温に１〜８時間保つことが必要であり、また貯蔵安
定性も十分であるとは言えない。またア建ンーＢ？、錯
体は一般に吸湿性が高く、堆扱いが困難であるばかシか
、得られ圧破化物の耐水性、耐薬品性、電気特性等の物
性がよくないという欠点を有する。An ideal catalyst would have good storage stability at room temperature and would cure quickly when heated, specifically within a few minutes, but to date, no satisfactory curing catalyst is known. However, in most cases, it had to be cured using two methods or by heating at high temperatures for a long time. Furthermore, amine-BP and complexes (e.g. monoethylamine-BF), which are well known as latent curing catalysts, start curing by heating, but in order to obtain a cured product with sufficient physical properties, It is necessary to maintain the product at a high temperature for 1 to 8 hours, and its storage stability cannot be said to be sufficient. Aken-B again? Generally, complexes have the disadvantage that they are highly hygroscopic and difficult to compost, and that the resulting crushed material has poor physical properties such as water resistance, chemical resistance, and electrical properties.
さらに硬化に際して十分な注意を行なわないと硬化物の
表面にしわがよってしまう。Furthermore, if sufficient care is not taken during curing, the surface of the cured product will wrinkle.
こうしたアミン−ＢＦ、錯体の欠点を改良した−のとし
て、ホワイト（Ｗ、１．Ｗｈｉｔｓｓ）の米ｍｓ許第５
５４５８４１号明細書にはア建ンーＰＦ、鐘体が述べら
れているが、同様に高温での硬化性は十分であるとは言
えない。As an improvement on the drawbacks of these amine-BF complexes, White (W, 1. Whitss), US MS No. 5
No. 545841 describes Aken-PF, but similarly, it cannot be said that the curing properties at high temperatures are sufficient.
ところで芳香族、脂肪族ないし脂環族のスルホニウム塩
は現在までもエポキシ樹脂と酸無水物硬化剤あるいはジ
シアンシア建ド硬化剤の組合せからなる系においての潜
在性のすぐれ九硬化促進削として知られている。しかし
このような場合は陰イ゛オン部分としてｏｔ−、Ｂｒ″
′、カルボキシレートなどの求核性陰イオンを有するス
ルホニウム塩を用いるのが好壕しく、酸無水−やジシア
ンシア建ド等の硬化剤を用いず、エポキシ樹脂とスルホ
ニウム塩だけを用い九場合にはエポキシ樹脂を硬化する
ことはで自ない。By the way, aromatic, aliphatic or alicyclic sulfonium salts are known to have excellent latent properties and to accelerate curing in systems consisting of a combination of epoxy resin and acid anhydride curing agent or dicyanthia curing agent. There is. However, in such a case, ot-, Br'' are used as anion parts.
It is preferable to use a sulfonium salt with a nucleophilic anion such as carboxylate, and in some cases, only an epoxy resin and a sulfonium salt are used without using a curing agent such as acid anhydride or dicyanthia. It is not natural to cure epoxy resin.
また非求核性の陰イオンとしてよく知られているＢＰ、
−塩は上記陰イオンの場合と異なシ、エポキシ樹脂を硬
化せしめることはできるが、本発明の特殊スルホニウム
塩の論イオン構成部分として使用し九場合硬化性及び硬
化物の物性の両面から本発明の目的には好ましくない。In addition, BP, which is well known as a non-nucleophilic anion,
-Salts can cure epoxy resins in a different way from the anions mentioned above, but when used as an ion component of the special sulfonium salt of the present invention, the present invention is advantageous from both the curability and the physical properties of the cured product. undesirable for this purpose.
スルホニウム塩は大別すると芳香族スルホニウム塩と脂
肪族あるいは脂環式スルホニウム塩がある。Sulfonium salts can be broadly classified into aromatic sulfonium salts and aliphatic or alicyclic sulfonium salts.
芳香族スルホニウム塩は一般に加熱による硬化性が乏し
く、例えばトリフェニルスルホニクム塩はアニオン部分
にＰＦ、−、ムＳ？Ｓ−中８ｂジローのような部分を有
するものでも硬化に際しては２００℃以上の温度を必要
とすゐ。そこでこうし九芳香族Ｏスルホニウム塩を利用
しエポキシ樹脂の硬化触媒として利用する方法として（
４）特公昭５２−１４２７８号公報には光エネルギーで
ルイス駿触媒を発生させえり、また別の方法として伸）
特開昭５４−１０２ｉ５９４号公報にはある種の還元剤
でスルホニウムカチオンのカチオン性を減少させルイス
酸を放出させる方法や（０）公表公報昭和５６年第５０
０２１８号には特殊の芳香族スルホニウム塩と酸化剤と
を組み合わせる方法が記載されている。Aromatic sulfonium salts generally have poor curing properties by heating; for example, triphenylsulfonicum salts have PF, -, S? in the anion moiety. Even those with a part like S-Medium 8B Giro require a temperature of 200°C or higher during curing. Therefore, there is a method of using this nine aromatic O sulfonium salt as a curing catalyst for epoxy resin (
4) Japanese Patent Publication No. 52-14278 describes a method for generating a Lewis-Shun catalyst using light energy, and also describes another method.
JP-A-54-102i594 describes a method of reducing the cationicity of sulfonium cations with a certain reducing agent and releasing Lewis acids, and (0) Publication No. 50 of 1982.
No. 0218 describes a method of combining special aromatic sulfonium salts with oxidizing agents.
スルホニウム塩が熱により分解するｍＦｉ党エネルギー
などの輻射エネルギーによる場合と機構が異な）分解生
成物も異なるのが通常であることは嘗うまでもないが、
一般の感光性スルホニウム−媒に光エネルギーに相当す
るだけの熱エネルギーを与えればルイス酸を放出するこ
とも可能ではある。It goes without saying that the decomposition products (the mechanism is different from those caused by radiant energy such as mFi energy, in which sulfonium salts are decomposed by heat), are usually different.
It is also possible to release a Lewis acid by applying heat energy equivalent to light energy to a general photosensitive sulfonium medium.
しかし熱硬化性樹脂をして使用する場合には、硬化の少
なくとも第１段階＃：ｔ１５０℃以下で行うのが好まし
く、ま九光感受性め強いスルホニウム塩は通常の雰囲気
下の光の条件下でも徐々にゲル化が進行し可使時間を短
縮する傾向がある。However, when used as a thermosetting resin, it is preferable to carry out at least the first stage of curing at a temperature of 150°C or lower. There is a tendency for gelation to progress gradually and shorten the pot life.
また、かかる芳香族スルホニウム塩を上記中）乃ｊｉｉ
（Ｃ）の方法で第５物質と並用する方法は可使時間を
短縮させること中破化時の発泡の問題があり得るばかシ
か、場合によってはエポキシ樹脂の物性を損なうおそれ
がある。In addition, such aromatic sulfonium salts)
Method (C) in which the fifth substance is used at the same time shortens the pot life, may cause problems with foaming during breakage, and in some cases may impair the physical properties of the epoxy resin.
一方脂肪族スルホエウム塩は比較的光に対して安定であ
り、熱に対して感受性を有する。しかしトリメチルスル
ホニウム塩のごとき単純なスルホニウム塩、は硬化に際
して１５０℃以上の加熱も要する仁とからかならずしも
好ましいと言えない。On the other hand, aliphatic sulfoneum salts are relatively stable to light and sensitive to heat. However, simple sulfonium salts such as trimethylsulfonium salts are not necessarily preferred because they require heating at 150° C. or higher during curing.
本発明者らはζうし良風状を考慮しつつ、満足な貯蔵安
定性（例えば室温６ケ月以上）と＾温での速硬化性（例
えば１５０℃ゲル化時間５分以内）を兼ね備えたしかも
吸湿性がなく硬化物の耐水性、耐薬品性、電気特性等の
物性が良好なカチオン重合触媒を広範囲に検討するうち
に、硫黄原子に対して脂肪族基の１つがα位に芳香族基
を有し、アニオン部分［ＰＦ−、ムｅＦ６−。The present inventors have developed a product that has both satisfactory storage stability (e.g., room temperature for 6 months or more) and fast curing at ^ temperature (e.g., gelation time at 150°C within 5 minutes) while taking into consideration the air quality. While extensively investigating cationic polymerization catalysts that are non-hygroscopic and have good physical properties such as water resistance, chemical resistance, and electrical properties for cured products, we found that one of the aliphatic groups was an aromatic group at the α-position relative to the sulfur atom. and has an anionic moiety [PF-, mueF6-.
８１）Ｆ、”’、 １３ｍ）（ＯＨ）？、−を有するス
ルホニウム塩が良好な陽イオン重合性有機物質の潜在性
カチオン重合触媒となシ得ることを発見し、本発明を完
成した。It was discovered that a sulfonium salt having 81) F, "', 13m) (OH)?, - can serve as a good latent cationic polymerization catalyst for cationically polymerizable organic substances, and the present invention was completed.
本発明の熱硬化性樹脂組成物は、必須の成分として
（１） 陽イオン重合性有機物質と、（２） 一般
式
（式中１１．Ｒ，は同−又は異なる置換又は非置換の脂
肪族又は脂環族基でＲ１，Ｒ２は環を形成していてもよ
い。ムはカチオン性イオウ原子に対してα位に６〜２０
の炭素原子を有する一価の芳香族基を一ヶ有する膨化水
素基、ＸはＰｌ ムＢν ８１）Ｆ ８ｂ（ＯＨ）
ＩＦ、から遺ばれる１ ６ｔ ６・
陰イオン）で表わされるスルホニウム塩とを含有する。The thermosetting resin composition of the present invention comprises (1) a cationically polymerizable organic substance as essential components, and (2) a compound of the general formula (11. Alternatively, R1 and R2 may form a ring in an alicyclic group.
a swollen hydrogen group having one monovalent aromatic group having a carbon atom, X is Pl Bν 81)F 8b(OH)
IF, a sulfonium salt represented by 1 6t 6 anion) left behind from IF.
本発明に用いられる陽イオン重合性有機物質（１）とし
ては酸重合性又は酸硬化性有機物質、とりわけエポキシ
樹脂が好ましく用いられる。As the cationically polymerizable organic substance (1) used in the present invention, acid-polymerizable or acid-curable organic substances, particularly epoxy resins, are preferably used.
本発明に使用されるエポキシ樹脂とは従来公知の芳香族
エポキシ樹脂、脂環族エポキシ樹脂。The epoxy resin used in the present invention is a conventionally known aromatic epoxy resin or alicyclic epoxy resin.
脂肪族エポキシ樹脂が挙げられる。ここで、芳香族エポ
キシ樹脂として特に好ましいものは、少なくとも１個の
芳香族核を有する多価フェノール又はそのアルキレンオ
キサイド付加体のポリグリシジルエーテルであって、例
えばビスフェノールＡ又はそのアルキレンオキサイド付
加体とエピクロルヒドリンとの反応によって製造される
グリシジルエーテル、エポキシノボラック樹脂が挙げら
れる。また脂環族エポキシ樹脂として４１に好ましいも
のとしては少なくとも１個の脂環を有する多価アルコー
ルのポリグリシジルエーテル又はシクロヘキセン又はシ
クロペンテン環含有化合物を過酸化水素、過駿勢の適当
な酸化剤でエポキシ化することによって得らるシクロヘ
キセンオキサイド又はシクロペンテンオキサイド含有化
合物がある。ポリグリシジルエーテルの代表例としては
、水素添加ビスフェノールＡ又はそのアルキレンオキサ
イド付加体とエピクロルヒドリンとの反応によって製造
されるグリシジルエーテルが挙げられる。Examples include aliphatic epoxy resins. Here, particularly preferable aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A or its alkylene oxide adducts and epichlorohydrin. Examples include glycidyl ether and epoxy novolac resin produced by reaction with Preferred alicyclic epoxy resins for 41 include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or compounds containing cyclohexene or cyclopentene rings, which are epoxied with hydrogen peroxide and a suitable oxidizing agent in excess. There are cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by Typical examples of polyglycidyl ethers include glycidyl ethers produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin.
さらに脂肪族エポキシ樹脂として特に好ましいものはＭ
肪族多価アルコール又はそのアルキレンオキサイド付加
物のポリグリシジルエーテルがあり、その代表例として
は、１．６−ヘキサンジオールのジグリシジルエーテル
、グリセリンのトリグリシジルエーテル、ポリエチレン
グリコールのジグリシジルエーテル、ポリプロピレング
リコールのジグリシジルエーテル、エチレングリコール
、フロピレンゲリコール、グリセリン等の脂肪族多価ア
ルコールに１種又は２種以上のアルキレンオキサイド（
エチレンオキサイド、プロピレンオキサイド）を付加す
ることにより得られるポリエーテルポリオールのポリグ
リシジルエーテルが挙げられる。さらに脂肪族高級アル
コールのモノグリシジルエーテル中フェノール、クレゾ
ール又はこれらにアルキレンオキサイドを付加する仁と
により得られるポリエーテルアルコールのモノグリシジ
ルエーテル勢も希釈剤として配合する事ができる。Furthermore, particularly preferable aliphatic epoxy resin is M
There are polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, typical examples of which are diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, diglycidyl ether of polyethylene glycol, and polypropylene glycol. of aliphatic polyhydric alcohols such as diglycidyl ether, ethylene glycol, phlopylene gellicol, and glycerin, and one or more alkylene oxides (
Examples include polyglycidyl ethers of polyether polyols obtained by adding ethylene oxide, propylene oxide). Furthermore, monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, or alkylene oxide to monoglycidyl ethers of aliphatic higher alcohols can also be blended as diluents.
本発明のエポキシ樹脂としてはこれらの芳香族エポキシ
樹脂、脂環族エポキシ樹脂又は脂肪族エポキシ樹脂を単
独で４使用することができるが、所値の性能に応じて適
当に配合することが望ましい。このようなエポキシ樹脂
としてはエポキシ当量が６０〜１０００のものが特に好
ましい。As the epoxy resin of the present invention, four of these aromatic epoxy resins, alicyclic epoxy resins, or aliphatic epoxy resins can be used alone, but it is desirable to mix them appropriately depending on the desired performance. As such an epoxy resin, one having an epoxy equivalent of 60 to 1000 is particularly preferable.
ｔた、本発明のその他の陽イオン−合性有機物質として
は、エピスルフィド檎脂、環状エーテル、ラクトン、ビ
ニルエーテル、フェノール／ホルムアルデヒド樹脂勢が
挙げられる。Other cationic organic substances of the present invention include episulfide resin, cyclic ethers, lactones, vinyl ethers, and phenol/formaldehyde resins.
かかる陽イオン重合性有機物質は単独あるい＃−１２種
以上の混合物として使用できる。Such cationically polymerizable organic substances can be used alone or as a mixture of 12 or more types.
本発明のスルホニウム塩は次の一般式〔！〕て示される
ものである。The sulfonium salt of the present invention has the following general formula [! ].
ここで１１．Ｒ，は同−又は相異なる置換ま九は非置換
の脂肪族又は脂環族基でＲ１＊Ｒ２Ｆｉ環を形成してい
て龜よい。またムはカチオン性イオウ原子に対して６位
に６乃至２０個の炭素原子を有すゐ一価の芳香族基を１
ケ有する炭化水素基である。これらの脂肪族基、脂環族
基、炭化水素基は基中に不飽和結合、アルコキシ基、ニ
トロ基、ハロゲン基、水酸基、カルボキシル基。Here 11. R, may be the same or different substituted groups, and (9) may be an unsubstituted aliphatic or alicyclic group forming an R1*R2Fi ring. In addition, the compound contains a monovalent aromatic group having 6 to 20 carbon atoms at the 6-position relative to the cationic sulfur atom.
It is a hydrocarbon group having . These aliphatic groups, alicyclic groups, and hydrocarbon groups have unsaturated bonds, alkoxy groups, nitro groups, halogen groups, hydroxyl groups, and carboxyl groups.
エステル基、エーテル基、シアノ基、カルボニル基、ス
ルホン基、チオエーテル１勢の官能置換基を含むことが
できる。また芳香族基は脂肪族基、アルコキシ基、ニト
ロ基、ハロゲン基。It can contain functional substituents such as ester groups, ether groups, cyano groups, carbonyl groups, sulfone groups, and thioether groups. Aromatic groups include aliphatic groups, alkoxy groups, nitro groups, and halogen groups.
水酸基、カルボキシル基、エステル基、シアノ基、カル
ボニル基、スルホン基、チオエーテル基等を含む基で置
換されていて本よいがニトロ基、カルボキシル基、エス
テル基、シアノ基。Substituted with a group containing a hydroxyl group, a carboxyl group, an ester group, a cyano group, a carbonyl group, a sulfone group, a thioether group, etc., preferably a nitro group, a carboxyl group, an ester group, a cyano group.
カルボニル基、スルホン基のような電子吸引性の基は硬
化速度の点からは好ましくない。を走逆にメトキシ基や
メチル基のくとき電子供与性の基は可使時間を短縮する
が、硬化速度を高めることができるため場合によっては
好んで使用される。芳香族基としては置換乃至非置換の
フｘ＝ル基が好ましく、芳香族基の炭素数が多い場合や
、フェニル基に置換基を３個以上有する場合は光感受性
が強くな）、通常光下での可使時間が短縮され好オしく
ない′。同様の理由で上記Ｒ，，Ｒ，が感光性の強い芳
香族基を含有するのも好ましくない。Ｘ″″はＰｙ−、
ムｓＦ、−、８’ｂＦ、−。Electron-withdrawing groups such as carbonyl groups and sulfone groups are not preferred from the viewpoint of curing speed. Electron-donating groups such as methoxy or methyl groups shorten pot life, but are preferred in some cases because they can increase curing speed. The aromatic group is preferably a substituted or unsubstituted fluor group, and if the aromatic group has a large number of carbon atoms or if the phenyl group has three or more substituents, it will be sensitive to light). The pot life at the bottom is shortened, which is not good. For the same reason, it is also undesirable for R, , R, above to contain a highly photosensitive aromatic group. X″″ is Py-,
musF, -, 8'bF, -.
８ｂ（ＯＨ）？、−、よ如好ｔＬ＜はム−Ｆ６−、８ｔ
ｌＦ６−である。ＢＦｌｌ−及びその他の非求核性アニ
オンも使用してもよいが硬化性、物性の視点からは好ま
しくない。8b (OH)? , -, yoyo tL< is mu-F6-, 8t
IF6-. BFll- and other non-nucleophilic anions may also be used, but are not preferred from the viewpoint of curability and physical properties.
ζうしたスルホニウム塩は、一般の芳香族スルホニウム
塩と異なル比歇的容１に合成され、例えば対応するスル
フィドをアルキルハライドと反応させハロゲン陰イオン
を有するスルホニウム塩も合成し、しかる後に対応する
ルイス酸（塩）と陰イオン交換を実施しても得られるし
、また直接的にスルフィドにトリエチルオキソニウムへ
キサフルオロホスフェートのごとき試薬を反応させるこ
とによ如好収率で合成することもできる。These sulfonium salts are synthesized in a chemical composition different from that of general aromatic sulfonium salts. For example, a sulfonium salt having a halogen anion is synthesized by reacting the corresponding sulfide with an alkyl halide, and then the corresponding sulfonium salt is synthesized. It can be obtained by performing anion exchange with a Lewis acid (salt), or it can also be synthesized in a good yield by directly reacting sulfide with a reagent such as triethyloxonium hexafluorophosphate. .
かかるスルホニウム塩として好ましいものはベンジルテ
トラメチレンスルホニウムへキサフルオロホスフェート
、ベンジルテトラメチレンスルホニウムへキサフルオロ
アルセ＄−）、ペンジルテトラメチレンスルホニウムヘ
キサフルオロアンチモネート、ｐ−メトキシベンジルテ
トラメチレンスルホニウムヘキナフルオロアンチモネー
ト、ｐ−メトキシベンジルテトラメチレンスルホニウム
へキサフルオロアルセネート、ｐ−＝）ｏベン’／＃？
）ラメチレンスルホニウムへキサフルオロアルセネート
、ｏ−ニトロベンジルテトラメチレンスルホニウムへキ
サフルオロアルセ＄−）、ベンジルジメチルスルホニウ
ム〜けフロオロアンチモネート、ベンジルジエチルスル
ホニウムへキサフルオロアンｆ％４−ト等が挙げられる
。Preferred examples of such sulfonium salts include benzyltetramethylenesulfonium hexafluorophosphate, benzyltetramethylenesulfonium hexafluoroarse$-), penzyltetramethylenesulfonium hexafluoroantimonate, and p-methoxybenzyltetramethylenesulfonium hequinafluoroantimonate. , p-methoxybenzyltetramethylenesulfonium hexafluoroarsenate, p-=)oben'/#?
) ramethylenesulfonium hexafluoroarsenate, o-nitrobenzyltetramethylenesulfonium hexafluoroarsenate), benzyldimethylsulfonium fluoroantimonate, benzyldiethylsulfonium hexafluoroanf%4-t, etc. It will be done.
本発明の熱硬化性組成物は陽イオン重合性有機物質（１
）１ｏＯ重量部に対して前記一般式［１］で表わされる
特殊スルホニウム塩（２）を好ましくは０，０５乃至１
５重量部、よシ好ましく ＦｉＯ，１乃至１０重量部含
有する。The thermosetting composition of the present invention has a cationic polymerizable organic substance (1
) The special sulfonium salt (2) represented by the general formula [1] is preferably added in an amount of 0.05 to 1 part by weight per 100 parts by weight.
It contains 5 parts by weight, preferably 1 to 10 parts by weight of FiO.
また陰イオンが８１１７−、 ａｔ）（０１１）？、”
’であゐ場合を除き陽イオン重合性有機物質（１）はそ
の中少なくとも１０重量−以上の割合で脂環式エポキシ
樹脂を含有するのが好ましい。Also, the anion is 8117-, at) (011)? ,”
Unless otherwise specified, the cationically polymerizable organic substance (1) preferably contains an alicyclic epoxy resin in an amount of at least 10% by weight.
かかる本発明の組成物は一般に２Ｓｔｌ：の粘度で１乃
至１．０００，０００センチボイズΩ液状あるいは高温
で流動性のある粉末もしくは同体の状態であるが、５０
℃乃ｊｉ１４１０℃に加熱することによ１ｌｉｓｏ分以
内に硬化反応が起ζｊ）、１５０℃乃憂それ以上でＦｉ
１秒〜秒分５分以内粘着性の硬化物を得ることができる
。The composition of the present invention is generally in the form of a liquid with a viscosity of 2 Stl: 1 to 1.000,000 centivoise Ω, or as a powder or the like which is fluid at high temperatures, but
By heating to 1410°C, a curing reaction occurs within 1liso minute (ζj), and at 150°C or higher, a hardening reaction occurs.
A sticky cured product can be obtained within 1 second to 5 minutes.
本発明の組成−には、さらにカチオン重合を損なわない
範囲で稀釈の九めの溶剤や改質の丸めの非反応性の樹脂
やプレポリマーを配釡することができる。ま九例えば電
気特性等の物性を改良すゐ目的などのため有機カルボン
酸や酸無−水物を使用し九シ、あるいはゴム弾性等の物
性ｔも九せるなどの目的でポリオールを混合するのもよ
い。The composition of the present invention may further contain a diluent solvent and a modified non-reactive resin or prepolymer within a range that does not impair cationic polymerization. For example, organic carboxylic acids or acid anhydrides may be used for the purpose of improving physical properties such as electrical properties, or polyols may be mixed for the purpose of improving physical properties such as rubber elasticity. Good too.
またプリプレグ等の製造や、他の目的の九めに本発明の
スルホニウム塩と併用して他の温度で硬化反応を行うこ
との可能な硬化剤乃至硬化触媒を配合するのもよい。Furthermore, for the production of prepregs and other purposes, it is also good to blend a curing agent or a curing catalyst that can be used in combination with the sulfonium salt of the present invention to carry out a curing reaction at other temperatures.
本発明・の組成物はさらに顔料、染料、増量剤。The composition of the present invention further includes pigments, dyes, and fillers.
離燃剤、静電防止剤、硬化促進剤、書着性改良剤、流れ
調整剤、界面活性剤表どと混合しても用いられる。また
配合物中に弱い塩基性含有する化合物を少量添加し可使
時間をより長くす本ことも場合によっては有用であろう
。これらの、添加剤の量は機能と硬化性のバランスで決
められるが、ζうした組成物は金属、木材、ゴム。It can also be used in combination with flame release agents, antistatic agents, curing accelerators, writing improvers, flow control agents, surfactants, etc. It may also be useful in some cases to add small amounts of weakly basic-containing compounds to the formulation to extend the pot life. The amount of these additives is determined by the balance between functionality and hardenability, but these additives are suitable for metals, wood, and rubber.
プラスチックス、ガラス、セラミック製品等に使用する
仁とができる。It can be used for plastics, glass, ceramic products, etc.
本発明組成物の具体的用途としては、例えば保■、ツヤ
出しワニス、インキ、塗料、接着剤。Specific uses of the composition of the present invention include, for example, adhesives, gloss varnishes, inks, paints, and adhesives.
絶縁材料、積層板、構造材料、′プリプレグ、ガラス繊
維等の強化繊維の含浸材料、成形材料。Insulating materials, laminates, structural materials, prepregs, materials impregnated with reinforcing fibers such as glass fibers, and molding materials.
とりわけ高速液状成形、注鑞材料、各種部品の封止材料
、結合材料などを挙げることができる。Among others, mention may be made of high-speed liquid molding, soldering materials, sealing materials for various parts, bonding materials, etc.
本発明の組成物は常温において可使時間が長く、１５０
℃以下の加熱によ如短時間で硬化し、高温硬化性にすぐ
れ、しかも吸湿性がなく、硬化物の耐水性、耐薬品性、
電気特性に優れた硬化物を与えることができる。The composition of the present invention has a long pot life at room temperature, and has a pot life of 150
It cures in a short time by heating below ℃, has excellent high-temperature curability, and has no moisture absorption, and the cured product has excellent water resistance, chemical resistance,
A cured product with excellent electrical properties can be provided.
以下実施例によって本発明の有効性を更に具体的に説明
するが本発明はその要旨を越えない限す以下の＊ｍ例に
制約されるものではない。EXAMPLES The effectiveness of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following *m examples as long as they do not go beyond the gist thereof.
実施例 １・″・□
ＩＲＩＩ−４２２１（脂環式エポキシ樹脂：ユニオンカ
ーバイド社製）１００重量部と種々のスルホニウム塩５
．０重量部からなる配合物をｌ１ｌＪ［Ｌ、各々約ｓ
ｏ ｏｑをとり、１５０℃に加熱した熱板−上（日新科
学株式会社製、ゲル化試験器ＧＴ−Ｄ！ｉＩりでゲル化
時間を測定した。結果を表ＩＫｔとめて示した。Example 1・″・□ 100 parts by weight of IRII-4221 (alicyclic epoxy resin: manufactured by Union Carbide) and various sulfonium salts 5
．． 0 parts by weight of l1lJ [L, each about s
The gelation time was measured using a gelling tester GT-D!iI (manufactured by Nissin Kagaku Co., Ltd.) on a hot plate heated to 150°C.The results are shown in Table IKt.
表 ！
実施例 ２
１１）−４１００（１１４電化製ビスフエノールム飄エ
ポキシ樹脂）１００重量部とペンジルテトラメチレンス
ルホニクム塩５重量部からなる組成物を少量ガラスビン
にとり１５０℃の油浴中で加熱し九ところ、その陰イオ
ン構成部分が／％ロゲン（ａｔ−、Ｂｒ−）の場合には
１時間後もさらさらした液体のｉｔであつ九。を九陰イ
オンがＢＰ、−の場合は１時間後増粘は見られたがまだ
未硬化のｔｔであった。しかし陰イオンが８ｂ１６″″
の場合は約２分でゲル化し強固な固体が得られ九。table ! Example 2 A small amount of a composition consisting of 100 parts by weight of 11)-4100 (bisphenolum epoxy resin manufactured by Denka Co., Ltd.) and 5 parts by weight of penzyltetramethylene sulfonicum salt was placed in a glass bottle and heated in an oil bath at 150°C. However, when the anion component is /% rogen (at-, Br-), it remains a free-flowing liquid even after 1 hour. When the nine anions were BP and -, thickening was observed after 1 hour, but the tt was still uncured. However, the anion is 8b16″″
In this case, it gels in about 2 minutes and a strong solid is obtained.
実施例 ５
ペンジルテトラメチレンスルホエウムヘキサフルオロア
ンチモネート１重量部とＩＩＲＬ−４２２１１００重量
部からなる組成物は１５０℃でゲル化時間１９秒という
優れ良熱硬化性を示すがガラスビン中に保存し、通常光
の謬囲気下富温に５ケ月以上放置してもたいした増粘は
見られなかつ九。ところがトリフェニルスルホニウムへ
キサフルオ賞アンチ毫ネート乃至は特開昭５４−１５１
？ＪＳ４号公報記載の感光性芳香族スルホニウム塩ｔ１
重量部含む同様の組成物は通常光の雰囲気下室源で数日
後にはつきりした増粘が見られ、場合によっては完全に
ゲル化することがあった。Example 5 A composition consisting of 1 part by weight of penzyltetramethylene sulfomeum hexafluoroantimonate and 100 parts by weight of IIRL-4221 showed excellent thermosetting properties with a gelation time of 19 seconds at 150°C, but it could not be stored in a glass bottle. No significant increase in viscosity was observed even after being left in a warm atmosphere under normal light for more than 5 months. However, triphenylsulfonium hexafluoro-prize antinate or JP-A-154-151
? Photosensitive aromatic sulfonium salt t1 described in JS4 publication
Similar compositions containing parts by weight exhibited significant thickening and, in some cases, complete gelation after several days in a room source under normal light.
実施例 ４
ペンジルテトラメチレンスルホニウムヘキサフルオ四ア
ンチモネート１重量部とＥＫＬ−４２２１１００重量部
を含む組成物を１００℃で２時間硬化せしめたところ強
固な硬化物が得られ九。Example 4 A composition containing 1 part by weight of penzyltetramethylenesulfonium hexafluorotetraantimonate and 100 parts by weight of EKL-4221 was cured at 100°C for 2 hours, and a strong cured product was obtained.
さらに１６０℃で後硬化を２時間以上行った硬化物は熱
変形温度１６０℃以上で耐水性、耐薬品性、電気特性に
優れたものであった。ところが一方ペンジルテトラメチ
レンスルホニウムテトラフルオμボレート５重量部とＥ
ＲＩ、−４２２１１００１量部とからなる同様の組成物
Ｆｉ硬化性が乏しく硬化にはよ如高温（１４０℃）を要
したが、得られた硬化物の物性は１６０℃で数時間後硬
化を行った後でも耐熱性、耐薬品性、耐水性９機械強度
、高温電気特性において良好ではなかった。Furthermore, the cured product which was post-cured at 160°C for 2 hours or more had a heat distortion temperature of 160°C or higher and was excellent in water resistance, chemical resistance, and electrical properties. However, on the other hand, 5 parts by weight of penzyltetramethylenesulfonium tetrafluoro μborate and E
A similar composition consisting of RI, -42211001 parts Fi had poor curability and required a much higher temperature (140°C) to cure, but the physical properties of the resulting cured product showed that after several hours of post-curing at 160°C. Even after drying, the heat resistance, chemical resistance, water resistance, mechanical strength, and high-temperature electrical properties were not good.
実施例 ５
ベンジルテトラメチレンスルホニウムへキサフルオロア
ル上ネート３重量ｌｌトｖｐＬ−＜２２１７０重量部と
！！！ＰＰＭ−２０１（日本化県展エポキシ化フェノー
ルノボラック）５０重量部からなる組成物を１０５℃２
時間硬化し、さらに１６０℃で４時間硬化せしめ九とこ
ろ、熱変形温度１９０℃の強固な電気特性に優れた硬化
物が得られた。この組成物の室温での貯蔵安定性は３ケ
月以上であった。Example 5 Benzyltetramethylene sulfonium hexafluoroalmonate 3 parts by weight to vpL-<22170 parts by weight! ! ! A composition consisting of 50 parts by weight of PPM-201 (Nippon Kakenten epoxidized phenol novolac) was heated at 105°C2.
After curing for a few hours and then curing for 4 hours at 160°C, a cured product with a heat distortion temperature of 190°C and excellent electrical properties was obtained. The storage stability of this composition at room temperature was over 3 months.
実施例 ６
ペンジルテトラメチレンスルホエウムヘキサフルオロア
ンチモネート１重量部を含む実施例４の組成物を軟鋼板
に塗布し同様に硬化した時の引張りせん断接着強さを測
定したとζろ２２０神／ａ−であった、。Example 6 The composition of Example 4 containing 1 part by weight of penzyltetramethylene sulfoum hexafluoroantimonate was applied to a mild steel plate and cured in the same manner, and the tensile shear adhesive strength was measured. /a-.
以上のように本発明の組成物はすぐれた硬！ヒ性と貯東
安定性を示し、硬化物の物性も優・妊たものが得られる
。As described above, the composition of the present invention has excellent hardness! It exhibits abrasion resistance and storage stability, and the cured product has excellent physical properties.
Claims (1)
肪族又は脂環族基で、Ｒ□、Ｒ２は環を形成していても
よい。ムはカチオン性イオウ原子に対してα位に６〜２
０の炭素原子を有する一価の芳香族基を一ヶ有する炭化
水素基、ＸはＰＦ、、 ＡｓＦ６． Ｂｂ’ｌ１６．８
ｂ（ＯＲ）ＩＦ、から選ばれる陰イオン）で表わされる
スルホニウム塩とを含有することを特徴とする熱硬化性
樹脂組成物。 ２、 Ｘｋホニウム塩カシアルキルベンジルスルホニ
ウムへキサフルオロアンチ毫ネート（２ケのアルキル基
は環を形成していてもよい）である特許請求の範囲第１
項記載の熱硬化性樹脂組成物。 ５、 スルホニウム塩が、ベンジル基に電子供与性の置
換基を有するジアルキル置換ペンジルスルホニウムヘキ
サフルオロアンチモネート（２ケのアルキル基は環を形
成していてもよい）である特許請求の範囲第２項記載の
熱硬化性樹脂組成物。[Scope of Claims] 1. As essential components: (1) a cationic polymerizable organic substance; In the cyclic group, R□ and R2 may form a ring.
a hydrocarbon group having one monovalent aromatic group having 0 carbon atoms, X is PF, AsF6. Bb'l16.8
b(OR)IF, an anion selected from IF). 2. Claim 1 which is Xk fonium salt casialkylbenzylsulfonium hexafluoroanthinate (two alkyl groups may form a ring)
The thermosetting resin composition described in . 5. Claim 2, wherein the sulfonium salt is dialkyl-substituted penzylsulfonium hexafluoroantimonate having an electron-donating substituent on the benzyl group (the two alkyl groups may form a ring). The thermosetting resin composition described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13502781A JPH0237924B2 (en) | 1981-08-28 | 1981-08-28 | NETSUKOKASEISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13502781A JPH0237924B2 (en) | 1981-08-28 | 1981-08-28 | NETSUKOKASEISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5837003A true JPS5837003A (en) | 1983-03-04 |
| JPH0237924B2 JPH0237924B2 (en) | 1990-08-28 |
Family
ID=15142220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13502781A Expired - Lifetime JPH0237924B2 (en) | 1981-08-28 | 1981-08-28 | NETSUKOKASEISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0237924B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01118564A (en) * | 1987-10-30 | 1989-05-11 | Toshiba Chem Corp | One-pack epoxy resin composition |
| EP0504569A2 (en) * | 1991-02-18 | 1992-09-23 | Siemens Aktiengesellschaft | Method of coating or sealing of electronic components or component groups |
| US5399596A (en) * | 1988-03-03 | 1995-03-21 | Sanshin Kagaku Kogyo Co., Ltd. | Polyfluoride sulfonium compounds and polymerization initiator thereof |
| US5447797A (en) * | 1992-08-10 | 1995-09-05 | Siemens Aktiengesellschaft | Reaction resin mixture comprising epoxy resin, benzylthiolanium salt and sensitizer |
| WO2007111092A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111075A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
| WO2007111074A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
| WO2014136900A1 (en) | 2013-03-08 | 2014-09-12 | 日立化成株式会社 | Ionic-compound-containing treatment solution, organic electronic element, and method for manufacturing organic electronic element |
-
1981
- 1981-08-28 JP JP13502781A patent/JPH0237924B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01118564A (en) * | 1987-10-30 | 1989-05-11 | Toshiba Chem Corp | One-pack epoxy resin composition |
| US5399596A (en) * | 1988-03-03 | 1995-03-21 | Sanshin Kagaku Kogyo Co., Ltd. | Polyfluoride sulfonium compounds and polymerization initiator thereof |
| EP0504569A2 (en) * | 1991-02-18 | 1992-09-23 | Siemens Aktiengesellschaft | Method of coating or sealing of electronic components or component groups |
| US5447797A (en) * | 1992-08-10 | 1995-09-05 | Siemens Aktiengesellschaft | Reaction resin mixture comprising epoxy resin, benzylthiolanium salt and sensitizer |
| WO2007111092A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111075A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
| WO2007111074A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
| WO2014136900A1 (en) | 2013-03-08 | 2014-09-12 | 日立化成株式会社 | Ionic-compound-containing treatment solution, organic electronic element, and method for manufacturing organic electronic element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0237924B2 (en) | 1990-08-28 |
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