JPS62179518A - Curing of vinyl ester resin and curing agent therefore - Google Patents
Curing of vinyl ester resin and curing agent thereforeInfo
- Publication number
- JPS62179518A JPS62179518A JP2017286A JP2017286A JPS62179518A JP S62179518 A JPS62179518 A JP S62179518A JP 2017286 A JP2017286 A JP 2017286A JP 2017286 A JP2017286 A JP 2017286A JP S62179518 A JPS62179518 A JP S62179518A
- Authority
- JP
- Japan
- Prior art keywords
- curing
- resin
- cobalt
- vinyl ester
- examples
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 14
- -1 peracid ester Chemical class 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 26
- 238000005187 foaming Methods 0.000 abstract description 13
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 abstract description 6
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 abstract description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 abstract description 4
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 abstract description 3
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 50
- 239000004342 Benzoyl peroxide Substances 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 1
- RDDUDYIRMHIYNO-UHFFFAOYSA-N 9-tert-butylperoxy-9-oxononanoic acid Chemical compound CC(C)(C)OOC(=O)CCCCCCCC(=O)O RDDUDYIRMHIYNO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 102100029290 Transthyretin Human genes 0.000 description 1
- 108050000089 Transthyretin Proteins 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は硬化剤、促進剤を添加した時、発泡が全くなく
、残存スチレン量の少い完全硬化物を与えるビニルエス
テル樹脂の硬化方法及び硬化剤に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method for curing vinyl ester resin that provides a completely cured product with no foaming and a small amount of residual styrene when a curing agent and an accelerator are added. Regarding hardening agents.
本発明でいうビニルエステルＭ−ｔ ＢＷは、不飽和エ
ポキシ樹脂、又はエポキシアクリレート樹脂ともいわれ
ているもので、一般的にはエポキシ樹脂のエポキシ基に
不飽和−塩基酸を開環付加させたもの、又はそれをスチ
レンのような重合性単量体に溶解させたものである。The vinyl ester M-t BW referred to in the present invention is also called an unsaturated epoxy resin or an epoxy acrylate resin, and is generally a ring-opening addition of an unsaturated basic acid to the epoxy group of an epoxy resin. , or it is dissolved in a polymerizable monomer such as styrene.
（従来の技術）
従来、ビニルエステル樹脂の常温硬化系としては、硬化
剤と硬化促進剤の組み合せが採用されている。具体的に
は囚メチルエチルケトンパーオキサイド（以下ＭＥＫＰ
Ｏと略ｆ）とコバルト系促進剤＋Ｅベンゾイルパーオキ
サイド（以下ＢＰＯと略す）とジメチルアニリン（以下
ＤＭＡと略す）が使用されている。(Prior Art) Conventionally, a combination of a curing agent and a curing accelerator has been adopted as a room temperature curing system for vinyl ester resin. Specifically, methyl ethyl ketone peroxide (MEKP)
O and f), a cobalt-based accelerator + E benzoyl peroxide (hereinafter abbreviated as BPO), and dimethylaniline (hereinafter abbreviated as DMA) are used.
（発明が解決しようとする問題点）
しかしながら、従来の硬化剤、促進剤の組み合せでビニ
ルエステル樹脂を硬化した場合それぞれ次の様な問題点
がある。(Problems to be Solved by the Invention) However, when vinyl ester resins are cured using conventional combinations of curing agents and accelerators, the following problems arise.
（Ａ） Ｍ Ｅ ｔ＜ ｐ Ｏとコバルト系促進剤Ｏ
樹脂にＭ Ｅ ｆ（Ｐ Ｏとコバルト系促進剤を混合す
ると発泡して作業が続けられない。(A) M E t< p O and cobalt-based accelerator O
If MEF (PO) and a cobalt-based accelerator are mixed with the resin, it will foam and the work cannot be continued.
０発泡により、樹脂が７全硬化しにくい。Due to zero foaming, the resin is difficult to completely cure.
（実際には、硬化樹脂中に多量のスチレンモノマーが残
存し硬度の低い硬化・物しか得られない）
ＦＢＩ ＢＰＯとＤＭＡ
ｏ樹脂にＢＰＯとＤＭＡを混合した場合発泡はないが、
硬化樹脂中の残存スチレンモノマーが、Ｍ Ｅ Ｋ Ｐ
Ｏとコバルト系促進剤の場合よりも多く、完全硬化し
にくい。(Actually, a large amount of styrene monomer remains in the cured resin, resulting in a cured product with low hardness.) FBI BPO and DMA o When BPO and DMA are mixed with the resin, there is no foaming, but
The residual styrene monomer in the cured resin is M E K P
The amount is higher than that of O and cobalt-based accelerators, making complete curing difficult.
０耐候性が悪い。特に硬化樹脂が、佳日的に黄変し、商
品価値がおちる。0 Poor weather resistance. In particular, cured resin turns yellow over time, reducing its commercial value.
本発明者らは、上記したような従来の硬化系に起因する
問題点を解決すべく研究した結果、硬化剤としてクメン
ハイドロパーオキサイド（以下ＣＨＰと略す）と過酸エ
ステル、促進剤としてコバルト系促進剤とアセト酢酸エ
ステルを組み合せて使用すれば、（］）樹脂添加時発泡
は全くおこらず、（２）硬化樹脂中の残存スチレン量が
非常に少なく、硬度の高い完全硬化物が得られ、（３）
経日的に変色のない耐候性に丁ぐれた硬化物が得られる
ことを見出し本発明に至った。As a result of research to solve the problems caused by the conventional curing systems as described above, the present inventors discovered that cumene hydroperoxide (hereinafter abbreviated as CHP) and peracid ester were used as curing agents, and cobalt-based curing systems were used as accelerators. If the accelerator and acetoacetate are used in combination, (]) no foaming will occur when the resin is added, (2) the amount of residual styrene in the cured resin is extremely small, and a completely cured product with high hardness can be obtained. (3)
It was discovered that a cured product with excellent weather resistance that does not discolor over time can be obtained, leading to the present invention.
即ち本発明は
（］）硬化剤としてクメンハイドロパーオキサイドと過
酸エステルを使用し、硬化促進剤として、コバルト系促
進剤とアセト酢酸エステルを使用することを％徴とする
ビニルエステル樹脂の硬化方法。That is, the present invention provides () a method for curing vinyl ester resin, which uses cumene hydroperoxide and a peracid ester as a curing agent, and uses a cobalt accelerator and acetoacetate as a curing accelerator. .
及び
（２） クメンハイドロパーオキサイドと過酸エステル
との混合物からなることを特徴とする硬化剤である。and (2) a curing agent characterized by comprising a mixture of cumene hydroperoxide and a peracid ester.
本発明に使用する過酸エステルは具体的には、ｔ−ブチ
ルパーオキシベンゾエート、ｔ−ブチルパーオキシオク
トエート、ｔ−アミルパーオキシベンゾエート、ｔ−ア
ミルパーオキシオクトエート、ｔ−ブチルパーオキシビ
バレート、ｔ−ブチルパーオキシネオデカノエート、ｔ
−ブチルパーオキシアセテート、ｔ−ブチルパーオキシ
３．５．５− ）リメチルヘキサノエート、ｔ−ブチル
パーオキシイソブチレート、ｔ−ブチルパーオキシアゼ
レート、ｔ−プチルパーオキシイソプロピルカーボネ−
）、１−ブチルパーオキシ５ｅｅ−ブチルカーボネート
等である。Specifically, the peracid esters used in the present invention include t-butylperoxybenzoate, t-butylperoxyoctoate, t-amylperoxybenzoate, t-amylperoxyoctoate, and t-butylperoxybenzoate. rate, t-butyl peroxyneodecanoate, t
-butylperoxyacetate, t-butylperoxy3.5.5-)limethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyazelate, t-butylperoxyisopropyl carbonate
), 1-butylperoxy 5ee-butyl carbonate, etc.
又、コバルト系促進剤は、ナフテン酸コバルト、オクテ
ン酸コバルト等をであり、アセト酢酸エステルは、アセ
ト酢酸メチル、アセト酢酸エチル等である。Further, cobalt-based accelerators include cobalt naphthenate, cobalt octenoate, etc., and acetoacetate esters include methyl acetoacetate, ethyl acetoacetate, etc.
ＣＨＰと過酸エステルの混合比は、ＣＨＰ／過酸エステ
ル＝】／９〜９／１の範囲でビニルエステル樹脂の硬化
において、残存スチレンモノマーｔ’＝減少させ、完全
硬化させる効果があるが、過酸エステルの配合が多くな
るに従って、ゲル化時間、硬化時間が長くなる。それ故
好ましくはＣＨＰ／過酸エステル＝２／８〜８／２の範
囲である。The mixing ratio of CHP and peracid ester is within the range of CHP/peracid ester =]/9 to 9/1, which has the effect of reducing the residual styrene monomer t' and completely curing the vinyl ester resin. As the amount of peracid ester increases, the gelation time and curing time become longer. Therefore, the ratio of CHP/peracid ester is preferably in the range of 2/8 to 8/2.
樹脂１００部に対する、硬化剤の添加量は混合硬化剤と
して、０．５〜３部が好ましい。The amount of the curing agent added is preferably 0.5 to 3 parts as a mixed curing agent with respect to 100 parts of the resin.
促進剤の添加量は、コバルト系促進剤は６％Ｍ度のもの
で、０．１〜２部、アセト酢酸エステルは０．１〜２部
が好ましい添加量である。The amount of the accelerator to be added is preferably 0.1 to 2 parts for the cobalt-based accelerator having a concentration of 6% M, and 0.1 to 2 parts for the acetoacetate.
ＣＨＰと過酸エステルは別々に樹脂中に加えても良いし
、前もって混合して混合硬化剤として樹脂中に加えても
よい。またＣＨＰと過酸エステルとアセト酢酸エステル
ヲ任意ａ”＞ 割合で混合しておき、これを樹脂中に加
えてもよい。CHP and peracid ester may be added to the resin separately, or they may be mixed in advance and added to the resin as a mixed curing agent. Alternatively, CHP, peracid ester, and acetoacetate may be mixed in an arbitrary ratio of a'' and then added to the resin.
（実施例） 以下、比較例、実施例により、本発明を説明する。(Example) The present invention will be explained below with reference to comparative examples and examples.
各例中、硬化剤の硬化特性の測定は、Ｊ Ｉ Ｓ −に
−６９０１の方法に従った。硬化樹脂の硬化度の尺度で
ある硬度については、バーパーコールマン製のバーコー
ル硬度計ＧＹ２Ｊ ９３４−１で測定し、残存スチレン
モノマーについては、硬化樹脂を小片に粉砕し、ＤＩＮ
−１６９４５の方法により、メチレンクロライドを抽出
液として１更用し、ガスクロマトグラフィーを用いて行
った。In each example, the curing properties of the curing agent were measured according to the method of JIS-6901. The hardness, which is a measure of the degree of curing of the cured resin, was measured using a Barcoll hardness meter GY2J 934-1 manufactured by Barper Coleman, and the residual styrene monomer was measured by crushing the cured resin into small pieces and measuring it using a DIN
-16945, using methylene chloride as an extract once and using gas chromatography.
比較例１〜】１゜
表−】ハ、ビニルエステル樹脂（昭和高分子社製、リポ
キシＲ−８０２）を、各種硬化系を利用して２５℃で硬
化させた場合の■硬化特性、■硬化剤添加時の発泡の状
況、■硬化樹脂中の残存スチレンモノマー量、■硬化１
１！（脂の硬度について示したものである。Comparative Example 1 ~] 1゜Table -] C. ■ Curing properties, ■ Curing when vinyl ester resin (Lipoxy R-802, manufactured by Showa Kobunshi Co., Ltd.) is cured at 25°C using various curing systems Foaming status when adding agent, ■ Amount of residual styrene monomer in cured resin, ■ Curing 1
1! (This shows the hardness of fat.
表−１中、比較例１．２はそれぞれ現在汎用のＭＥＫＰ
Ｏ／コバルト系促進剤ＢＰＯ／ＤＭＡ硬化系について示
したものである。In Table 1, Comparative Examples 1 and 2 are currently general-purpose MEKPs.
This is shown for the O/cobalt accelerator BPO/DMA curing system.
ＭＥＫＰ／コバルト系促進剤の場合、硬化剤添加時の発
泡が激しく、２５℃で］週間硬化後のｍＪＩＷ中の残存
スチレンモノマー量も６．５％と高く、硬度は３０と低
く、硬化は完全とは言えない。又、通常、樹脂を完全硬
化させるために、温Ｖ＝かけて、後硬化をするが、この
場合、８０℃で２時間後硬化しても、残存スチレンモノ
マー量の減少は少なく、完全硬化には史に時間をか為る
必要がある。In the case of MEKP/cobalt-based accelerator, foaming was intense when the curing agent was added, and the amount of residual styrene monomer in mJIW after curing for weeks at 25°C was as high as 6.5%, the hardness was as low as 30, and curing was not complete. It can not be said. In addition, usually, in order to completely cure the resin, post-curing is performed by applying a temperature V=, but in this case, even after post-curing at 80°C for 2 hours, the amount of residual styrene monomer does not decrease much, and it is not possible to completely cure the resin. needs to take time to learn about history.
ＢＰＯ／ＤＭＡの場合、硬化剤添加時の発泡は全くない
けれど、残存スチレンモノマー量は、２５℃−】週間硬
化後８．８％、さらに８０℃＝２時間後硬化しても６．
５％と非常に高く、硬度も２５と低く硬化は不完全であ
る。In the case of BPO/DMA, there is no foaming when the curing agent is added, but the amount of residual styrene monomer is 8.8% after curing for 2 hours at 25°C, and 6.8% after curing for 2 hours at 80°C.
The hardness is extremely high at 5%, and the hardness is low at 25, meaning that the hardening is incomplete.
比較例３〜】】は、本発明で組み合せて使用する、ＣＨ
Ｐと過酸エステルをそれぞれ単独に使用して硬化させた
場合である。Comparative Example 3 ~ ] is used in combination in the present invention, CH
This is a case where P and peracid ester are used alone for curing.
ＣＨＰ、過酸エステルをそれぞれ単独で明脂に添加し、
促進剤としてナフテン酸コバルトａｎｄ１０「アセト酢
酸エステルを添加した場合、いずれも発泡はないが、硬
化樹脂の残存スチレンモノマー量は高くパーコール硬度
が低いことかられかるように、硬化は不完全であった。CHP and peracid ester are each added individually to clear resin,
When cobalt naphthenate and 10 acetoacetate were added as accelerators, there was no foaming in either case, but curing was incomplete, as evidenced by the high amount of residual styrene monomer in the cured resin and low Percoll hardness. .
特に過酸エステル単独使用の場合は、ゲル化時間が非常
に長く、常温で使用することは不可能であった。In particular, when a peracid ester is used alone, the gelation time is extremely long, making it impossible to use it at room temperature.
（略号の説明）
ＭＥＫＰ：メチルエチルケトンパーオキサイド（カヤメ
ックＭ 化薬ヌーリー社製→
Ｂｐｏ ：ベンゾイルパーオキサイド５０％ペースト
（カドノクスＢ−５０Ｐ 化薬ヌーリー社製）ＣＩＩ
Ｉ） ：クメンハイドロパーオキサイド（カヤクメン
ＦＩ 化薬ヌーリー社裂ンＴＢＰＢ： ｔ−ブチルパー
オキシベンゾエート（カヤブチルＢ 化薬ヌーリー社製
）
ＴＢＰＯ：ｔ−ブチルパーオキシオクトエート（カヤエ
ステル０ 化薬ヌーリー社製）ＴＢＮＤ：ｔ−ブチルパ
ーオキシネオデカノエート（トリボノックス２３ 化薬
ヌーリー社製）ＴＢＰＡ：ｔ−ブチルパーオキシアセテ
ート（カヤブチルＡ 化薬ヌーリー社製）
ＴＡＰＢ：ｔ−アミルパーオキシベンゾエート（トリボ
ノックス］２７ 化薬ヌーリー社製）Ｃｏ：ナフテン酸
コバル）（純度６％）ＤＭＡ ：Ｎ、Ｎ−ジメチルア
ニリンＧＴ ；ゲル化時間、ＣＴ：硬化時間、ＰＥＴ：
最高発熱温度Ｒ３（ａｌ ：２５℃−１週間硬化後の
樹脂中の残存スチレン量Ｉｔｓ（ｂｌ ：２５°Ｃ−
１週間→８０°Ｃ−２時間硬化後の樹脂中の残存スチレ
ン量
パーコール硬度二２５°Ｃ−１週間硬化後の硬度実施例
１〜１１゜
表−２は、ビニルエステル樹脂（昭和高分子社製、１ｌ
−８０２）にＣＨＰ／過虐エステル／アセト酢酸エステ
ル７ａｌ−使用してコバルト促進剤存在下で硬化した場
合の硬化特性、発泡の有無、硬化樹脂中の残存スチレン
モノマー量、パーコール硬度を示したものである。(Explanation of abbreviations) MEKP: Methyl ethyl ketone peroxide (Kayamek M, manufactured by Kayaku Noory Co., Ltd. → Bpo: Benzoyl peroxide 50% paste (Kadonox B-50P, manufactured by Kayaku Noory Co., Ltd.) CII
I): Cumene hydroperoxide (Kayakumen FI, manufactured by Kayaku Nouri Co., Ltd.) TBPB: t-butyl peroxybenzoate (Kayabutyl B, manufactured by Kayaku Nouri Co., Ltd.) TBPO: t-butyl peroxyoctoate (Kaya Ester 0, manufactured by Kayaku Nouri Co., Ltd.) ) TBND: t-butyl peroxyneodecanoate (Tribonox 23, manufactured by Kayaku Nury Co., Ltd.) TBPA: t-butyl peroxyacetate (Kayabutyl A, manufactured by Kayaku Nury Co., Ltd.) TAPB: t-amyl peroxybenzoate (Tribonox 23, manufactured by Kayaku Nury Co., Ltd.) Nox] 27 manufactured by Kayaku Nury Co., Ltd.) Co: cobal naphthenate) (purity 6%) DMA: N,N-dimethylaniline GT; gelling time, CT: curing time, PET:
Maximum exothermic temperature R3 (al: 25°C - Amount of styrene remaining in the resin after curing for 1 week Its (bl: 25°C -
1 week → 80°C - Amount of remaining styrene in the resin after curing for 2 hours Percoll hardness 2 Hardness after curing for 1 week at 25°C Examples 1 to 11° Made in Japan, 1l
-802) showing the curing characteristics, presence or absence of foaming, amount of residual styrene monomer in the cured resin, and Percoll hardness when cured in the presence of a cobalt accelerator using CHP/violent ester/acetoacetate 7al- It is.
実施例１〜５はＣＨＰ／ｌ−ブチルパーオキシベンゾエ
ート／アセト酢酸エチル／ナフテン酸コバルトを併用し
た場合である。硬化剤とアセト酢酸エチルを樹脂に添加
した場合、発泡は全く生じないし、２５℃におけるゲル
化、硬化時間も、従来のＭＥＫＰ ／コバルト系促進剤
、ＢＰＯ／ＤＭＡと同等で、調整も容易である。又、硬
化樹脂中の残存スチレンモノマー量は、２５°Ｃ−１週
間後で２％以下と非常に少なく、８０℃−２時間後硬化
後では、０，１％以下と完全硬化物が得られた。パーコ
ール硬度も４５と硬化が完全であることを示している。Examples 1 to 5 are cases where CHP/l-butylperoxybenzoate/ethyl acetoacetate/cobalt naphthenate were used in combination. When the curing agent and ethyl acetoacetate are added to the resin, no foaming occurs, and the gelation and curing times at 25°C are the same as those of conventional MEKP/cobalt accelerators and BPO/DMA, and are easy to adjust. . In addition, the amount of residual styrene monomer in the cured resin is very small, less than 2% after 1 week at 25°C, and less than 0.1% after 2 hours of curing at 80°C, meaning that a completely cured product cannot be obtained. Ta. Percoll hardness was also 45, indicating complete curing.
実施例６，７は、ＣＨＰ／ｌ−ブチルパーオキシベンゾ
エートにアセト酢酸メチルを併用した場合である。実施
例８〜１１は、硬化剤としてＣＨＰＫ種々の過酸エステ
ルを併用し、補助促進剤としてアセト酢酸エチルを併用
した場合を示している。いずれの実施例についても、樹
脂の発泡は無く、樹脂硬化物中の残存スチレンモノマー
量は少なく、パーコール硬度は高く、硬化度の高い樹脂
硬化物が得られた。Examples 6 and 7 are cases in which methyl acetoacetate was used in combination with CHP/l-butylperoxybenzoate. Examples 8 to 11 show cases in which various peracid esters of CHPK were used as a curing agent and ethyl acetoacetate was used as an auxiliary accelerator. In all Examples, there was no foaming of the resin, the amount of residual styrene monomer in the cured resin product was small, the Percoll hardness was high, and a cured resin product with a high degree of curing was obtained.
（発明の効果〕 実施例に示したように、本発明に示すＣＨＰ。(Effect of the invention〕 As shown in the examples, CHP shown in the present invention.
過酸エステルとアセト酢酸エステルを硬化系としてコバ
ルト系促進剤存在下、ビニルエステル樹脂を硬化させた
場合、従来のＭＥＫＰ ／コバルト系促進剤、ＢＰＯ／
ＤＭＡ硬化系に比較して、添加時、樹脂の発泡が全（な
く、作業性が良好であり、完全硬化して、すぐれた樹脂
硬化物が得られることがわかる。When vinyl ester resin is cured using a peracid ester and acetoacetate as a curing system in the presence of a cobalt-based accelerator, conventional MEKP/cobalt-based accelerator, BPO/
It can be seen that, compared to the DMA curing system, there is no foaming of the resin upon addition, the workability is good, and the resin is completely cured to give an excellent cured resin product.
本発明の硬化系を使用した硬化方法によりビニルエステ
ル樹脂本来のすぐれた特性を最大限に発現することがで
き、工業的価値は極めて大きい。The curing method using the curing system of the present invention allows the original excellent characteristics of vinyl ester resin to be expressed to the maximum extent, and is of extremely great industrial value.
Claims (2)
酸エステルを使用し、硬化促進剤として、コバルト系促
進剤とアセト酢酸エステルを使用することを特徴とする
ビニルエステル樹脂の硬化方法。(1) A method for curing vinyl ester resin, which comprises using cumene hydroperoxide and peracid ester as a curing agent, and using a cobalt accelerator and acetoacetate as a curing accelerator.
の混合物からなることを特徴とする硬化剤。(2) A curing agent comprising a mixture of cumene hydroperoxide and peracid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020172A JPH0617434B2 (en) | 1986-02-03 | 1986-02-03 | Method for curing vinyl ester resin and curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020172A JPH0617434B2 (en) | 1986-02-03 | 1986-02-03 | Method for curing vinyl ester resin and curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62179518A true JPS62179518A (en) | 1987-08-06 |
| JPH0617434B2 JPH0617434B2 (en) | 1994-03-09 |
Family
ID=12019755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61020172A Expired - Lifetime JPH0617434B2 (en) | 1986-02-03 | 1986-02-03 | Method for curing vinyl ester resin and curing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0617434B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441987A (en) * | 1977-09-09 | 1979-04-03 | Nippon Oil & Fats Co Ltd | Curing of vinyl ester resin |
-
1986
- 1986-02-03 JP JP61020172A patent/JPH0617434B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441987A (en) * | 1977-09-09 | 1979-04-03 | Nippon Oil & Fats Co Ltd | Curing of vinyl ester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0617434B2 (en) | 1994-03-09 |
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