JPH0623240B2 - Curing accelerator for epoxy resin - Google Patents
Curing accelerator for epoxy resinInfo
- Publication number
- JPH0623240B2 JPH0623240B2 JP29565386A JP29565386A JPH0623240B2 JP H0623240 B2 JPH0623240 B2 JP H0623240B2 JP 29565386 A JP29565386 A JP 29565386A JP 29565386 A JP29565386 A JP 29565386A JP H0623240 B2 JPH0623240 B2 JP H0623240B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing
- curing accelerator
- compound
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 10
- 229920000647 polyepoxide Polymers 0.000 title claims description 10
- -1 guanidine compound Chemical class 0.000 claims description 10
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 150000002357 guanidines Chemical class 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、エポキシ樹脂の硬化促進剤に関する。更に詳
しくは、酸無水物類、フェノールノボラック類などを硬
化剤として用いるエポキシ樹脂の硬化促進剤に関する。TECHNICAL FIELD The present invention relates to a curing accelerator for an epoxy resin. More specifically, it relates to a curing accelerator for an epoxy resin using an acid anhydride, a phenol novolac, etc. as a curing agent.
エポキシ樹脂の硬化促進剤として、たとえば１，８−ジ
アザビシクロ（５，４，０）ウンデセン−７（サンアプ
ロ株式会社製ＤＢＵ ）の如きアミジン化合物が知られ
ており、特に硬化剤を配合したエポキシ樹脂の硬化促進
剤として広く用いられている。グアニジン化合物につい
ても、すでに古くからテトラメチルグアニジンの如き化
合物が硬化促進剤として知られている〔たとえば、Ｊｏ
ｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ
Ｓｃｉｅｎｃｅ、９，２７０７（１９６５）〕。しか
し、これらのグアニジン化合物は硬化促進効果が小さ
く、また硬化物の物性などに問題点を有している。 As an epoxy resin curing accelerator, for example, 1,8-diene
Azabicyclo (5,4,0) undecene-7 (San Up
DBU made by b. ) Amidine compounds such as
In particular, it accelerates the curing of epoxy resin containing a curing agent.
Widely used as an agent. About guanidine compounds
However, it has already been used for a long time like tetramethylguanidine.
Compounds are known as curing accelerators [eg, Jo
urnal of Applied Polymer
Science,9, 2707 (1965)]. Only
However, these guanidine compounds have a small hardening accelerating effect.
In addition, there are problems in the physical properties of the cured product.
本発明者らは、上記の問題点を解決すべく鋭意検討した
結果、式(1)で示されるグアニジン化合物、またはその
塩類が優れた効果を有していることを見い出し、本発明
を完成した。The present inventors, as a result of intensive studies to solve the above problems, found that the guanidine compound represented by the formula (1) or a salt thereof has an excellent effect, and completed the present invention. .
（式中、Ｒ１，Ｒ２はそれぞれ任意に水素、またはメチ
ル基であり、Ｒ３は炭素数１ないし８のアルキル基、ベ
ンジル基、ヒドロキシエチル、またはプロピル基、シア
ノエチル基である。ｍ，ｎは２ないし４の整数であ
る。） 本発明のグアニジン化合物としては、たとえば下記の構
造式のものが挙げられる。 (In the formula, R 1 and R 2 are each independently hydrogen or a methyl group, and R 3 is an alkyl group having 1 to 8 carbon atoms, a benzyl group, hydroxyethyl, or a propyl group, a cyanoethyl group. M, n is an integer of 2 to 4.) Examples of the guanidine compound of the present invention include those having the following structural formulas.
〔７−メチル−１，５，７−トリアザビシクロ（４，
４，０）デセン−５、以下ＴＢＤ−Ｍｅと略記する。〕 （以下、ＴＢＤ−ＣＮと略記する。）−ＣＨ２ＣＨ２Ｏ
Ｈ，または これらのグアニジン化合物の合成方法については、すで
に古くから知られている。たとえば、Ｊ．Ｃｈｅｍ．Ｓ
ｏｃ．ＰＥＲＫＩＮ ＴＲＡＮＳ．Ｉ，２０８５（１９
８２）などに記載されている。本発明においては、その
合成方法については特に限定されず、たとえば、ＴＢＤ
−ＣＮの如きシアノエチル基を有する化合物にあつて
は、下記の構造式(2)で示されるグアニジン化合物とア
クリロニトリルを公知の方法で反応させて容易に得るこ
とができる。 [7-methyl-1,5,7-triazabicyclo (4,
4,0) decene-5, hereinafter abbreviated as TBD-Me. ] (Hereinafter, abbreviated as TBD-CN.) - CH 2 CH 2 O
H, or Methods for synthesizing these guanidine compounds have been known for a long time. For example, J. Chem. S
oc. PERKIN TRANS. I, 2085 (19
82) and the like. In the present invention, the synthesis method is not particularly limited.
A compound having a cyanoethyl group such as —CN can be easily obtained by reacting a guanidine compound represented by the following structural formula (2) with acrylonitrile by a known method.
〔１，５，７−トリアザビシクロ（４，４，０）デセン
−５、以下ＴＢＤと略記する。〕 本発明のグアニジン化合物の塩類は、グアニジン化合物
と広義の酸類、たとえばオクチル酸、トリメリツト酸、
フエノール、フエノールノボラツク、あるいはベンゾト
リアゾールの如きものとを反応させ、液状、固状、もし
くは粉末状のものとして容易に得ることができる。 [1,5,7-Triazabicyclo (4,4,0) decene-5, hereinafter abbreviated as TBD. The salts of the guanidine compound of the present invention include guanidine compounds and a wide range of acids such as octylic acid, trimellitic acid,
It can be easily obtained as a liquid, a solid, or a powder by reacting with a compound such as phenol, phenol novolac, or benzotriazole.
本発明のグアニジン化合物、またはその塩類は、硬化剤
としてたとえば、各種の酸無水物類、あるいはフェノー
ルノボラック類を用いるエポキシ樹脂の硬化促進剤とし
て用いられる。エポキシ化合物としては、たとえば、ビ
スフエノールＡ型、クレゾールノボラック型、あるいは
脂環型エポキシ化合物のごときすでに公知のものがあげ
られる。また、充填剤、滑剤、あるいは着色剤などの添
加剤が配合されたコンパウンドであつてもよいことはい
るまでもない。その添加量はエポキシ化合物１００重量
部に対して通常０．１ないし２５重量部、好ましくは
０．３ないし１５重量部である。さらに、液状、あるい
は粉体のコンパウンドのいずれにも使用でき、これらに
対する添加方法などは特に限定されない。The guanidine compound of the present invention or a salt thereof is used as a curing agent, for example, as a curing accelerator for an epoxy resin using various acid anhydrides or phenol novolacs. Examples of the epoxy compound include known compounds such as bisphenol A type, cresol novolac type, and alicyclic type epoxy compounds. Further, it goes without saying that a compound containing additives such as a filler, a lubricant or a colorant may be used. The amount added is usually 0.1 to 25 parts by weight, preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the epoxy compound. Further, it can be used as either a liquid compound or a powder compound, and the addition method thereof is not particularly limited.
以下、実施例および試験例により本発明を説明するが、
本発明はこれらに限定されるものではない。Hereinafter, the present invention will be described with reference to Examples and Test Examples.
The present invention is not limited to these.
実施例１．〜４．，比較例１．〜２．，参考例１．〜
２． ＴＢＤ−Ｍｅは、Ｆｌｕｋａ ＡＧ．製のものを蒸留精
製して用いた。ＴＢＤ−ＣＮは、Ｆｌｕｋａ ＡＧ．製
ＴＢＤを触媒にＫＯＨを用いてアクリロニトリルと反応
させ、触媒を中和除去して精製したものを用いた。ＴＢ
Ｄ−Ｍｅのオクチル酸塩およびフェノールノボラック塩
は、それぞれ、反応温度５０〜７０℃および１６０〜１
９０℃で、オクチル酸あるいはフェノールノボラックと
反応させたものを用いた。比較例１．〜２．および参考
例１．〜２．の硬化促進剤は試薬、または市販のものを
使用した。これらの硬化促進剤を表１．に示す。Example 1. ~ 4. Comparative Example 1. ~ 2. Reference Example 1. ~
2. TBD-Me is manufactured by Fluka AG. A product manufactured by distillation was used after being purified. TBD-CN is manufactured by Fluka AG. The TBD manufactured was reacted with acrylonitrile using KOH as a catalyst, and the catalyst was neutralized and removed to be purified. TB
D-Me octylate and phenol novolac salts have reaction temperatures of 50-70 ° C. and 160-1 respectively.
The one reacted with octylic acid or phenol novolac at 90 ° C. was used. Comparative Example 1. ~ 2. And Reference Example 1. ~ 2. The curing accelerator used was a reagent or a commercially available one. These curing accelerators are listed in Table 1. Shown in.
試験例（エポキシ樹脂の硬化促進試験）。 Test example (curing acceleration test of epoxy resin).
下記の配合処方で、酸無水物硬化、エポキシ単独硬化、
ならびにフェノールノボラック硬化のゲルタイム（試験
管法、または熱板法、所定の温度による。）を測定し、
硬化促進性を試験した。With the following formulation, acid anhydride cure, epoxy alone cure,
And the gel time of phenol novolac curing (test tube method or hot plate method, according to a predetermined temperature),
The cure acceleration was tested.
さらに、酸無水物硬化（硬化促進剤１部）については、
配合物を１０５℃×１時間＋１５０℃×４時間の条件で
ほぼ完全に硬化させ、Ｔｇ（ガラス転移温度、ＴＭＡ
法）および硬化物の着色度（目視）を測定した。一方、
フェノールノボラック硬化（硬化促進剤２部）について
は、配合物を１５０℃×２時間＋１８０℃×８時間の条
件でほぼ完全に硬化させ、Ｔｇを測定した。これらの結
果を表２．，表３．，および表４．に示す。Furthermore, regarding acid anhydride curing (1 part of curing accelerator),
The compound was almost completely cured under the conditions of 105 ° C x 1 hour + 150 ° C x 4 hours, and the Tg (glass transition temperature, TMA
Method) and the degree of coloring (visual inspection) of the cured product. on the other hand,
For the phenol novolac cure (2 parts cure accelerator), the formulations were almost completely cured under the conditions of 150 ° C x 2 hours + 180 ° C x 8 hours and the Tg was measured. These results are shown in Table 2. , Table 3. , And Table 4. Shown in.
酸無水物硬化： 表２．，表３．，および表４．に示すとおり、本発明の
グアニジン化合物、またはその塩類、エポキシ化合物単
独に対してはマイルドな硬化促進作用を有し、硬化剤を
配合したエポキシ化合物と硬化剤との共重合（硬化）の
系において高い硬化促進作用を有し、色相ならびにＴｇ
の優れた硬化物を提供する。Acid anhydride curing: Table 2. , Table 3. , And Table 4. As shown in, the guanidine compound of the present invention, or a salt thereof, has a mild curing accelerating effect on the epoxy compound alone, and in the system of copolymerization (curing) of the curing agent-blended epoxy compound and the curing agent. Has a high curing acceleration effect, hue and Tg
To provide an excellent cured product.
本発明のグアニジン化合物、またはその塩類は、特に、
硬化剤を配合したエポキシ樹脂の硬化に対して優れた促
進作用を有し、優れた硬化物を提供する。多品種、多機
能、さらにより優れた硬化性、あるいは硬化物性の要求
されるエポキシ樹脂の硬化促進剤として極めて有用なも
のである。The guanidine compound of the present invention, or a salt thereof, is particularly preferably
It has an excellent accelerating effect on the curing of an epoxy resin containing a curing agent, and provides an excellent cured product. It is extremely useful as a curing accelerator for an epoxy resin that requires a wide variety of products, multiple functions, and further excellent curability or cured physical properties.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−243085（ＪＰ，Ａ) 特開 昭58−57427（ＪＰ，Ａ) 特開 昭49−99699（ＪＰ，Ａ) 特開 昭61−12724（ＪＰ，Ａ) 米国特許4328330（ＵＳ，Ａ) ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-61-243085 (JP, A) JP-A-58-57427 (JP, A) JP-A-49-99699 (JP, A) JP-A-61- 12724 (JP, A) US Patent 4328330 (US, A)
Claims (1)
物、またはその塩類からなるエポキシ樹脂の硬化促進
剤。 （式中、Ｒ１，Ｒ２はそれぞれ任意に水素、またはメチ
ル基であり、Ｒ３は炭素数１ないし８のアルキル基、ベ
ンジル基、ヒドロキシエチルまたはプロピル基、シアノ
エチル基である。ｍ，ｎは２ないし４の整数である。）1. A curing accelerator for an epoxy resin, which comprises a guanidine compound represented by the following general formula (1) or a salt thereof. (In the formula, R 1 and R 2 are each independently hydrogen or a methyl group, and R 3 is an alkyl group having 1 to 8 carbon atoms, a benzyl group, a hydroxyethyl or propyl group, or a cyanoethyl group. M, n Is an integer of 2 to 4.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29565386A JPH0623240B2 (en) | 1986-12-10 | 1986-12-10 | Curing accelerator for epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29565386A JPH0623240B2 (en) | 1986-12-10 | 1986-12-10 | Curing accelerator for epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63146919A JPS63146919A (en) | 1988-06-18 |
| JPH0623240B2 true JPH0623240B2 (en) | 1994-03-30 |
Family
ID=17823430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29565386A Expired - Lifetime JPH0623240B2 (en) | 1986-12-10 | 1986-12-10 | Curing accelerator for epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623240B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100516409B1 (en) | 1998-02-19 | 2005-09-23 | 히다치 가세고교 가부시끼가이샤 | Novel compounds, hardening accelerator, resin composition, and electronic part device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328330A (en) | 1980-05-10 | 1982-05-04 | Bayer Aktiengesellschaft | Process for the production of polyureas |
-
1986
- 1986-12-10 JP JP29565386A patent/JPH0623240B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328330A (en) | 1980-05-10 | 1982-05-04 | Bayer Aktiengesellschaft | Process for the production of polyureas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63146919A (en) | 1988-06-18 |
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