JPH01266120A - Heat-resistant vinyl ester resin composition - Google Patents
Heat-resistant vinyl ester resin compositionInfo
- Publication number
- JPH01266120A JPH01266120A JP9533288A JP9533288A JPH01266120A JP H01266120 A JPH01266120 A JP H01266120A JP 9533288 A JP9533288 A JP 9533288A JP 9533288 A JP9533288 A JP 9533288A JP H01266120 A JPH01266120 A JP H01266120A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- parts
- acrylate
- meth
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 27
- 229920001567 vinyl ester resin Polymers 0.000 title claims description 15
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 13
- 229920003986 novolac Polymers 0.000 abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 10
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 239000004843 novolac epoxy resin Substances 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- -1 glycidyl ester Chemical class 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- 229930185605 Bisphenol Natural products 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱性の政所されたビニルエステル樹脂組成物
に関するものであり、更に詳しくはノボラック型エポキ
シアクリレートを主成分としスチレン及びジビニルベン
ゼンを含有するビニルエステル樹脂組成物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a heat-resistant polyvinyl ester resin composition, more specifically a composition containing novolac type epoxy acrylate as a main component and containing styrene and divinylbenzene. This invention relates to a vinyl ester resin composition.
（従来技術と解決すべき課題） 従来ビニルエステル樹脂は、優れた機械的特性。(Conventional technology and issues to be solved) Conventional vinyl ester resins have excellent mechanical properties.
電気的特性、耐熱性及び高接着性と良好な成形加工作業
性を兼ね備え、更に耐薬品性特に耐酸化性に優れている
ので、化学装置材Ｔ１殊にガラス繊維等のＶ＆維で強化
された耐食ｗ４雑強化プラスチック（耐食ＦＲＰ）のマ
トリックス（母材）として広く利用され、例えば化学工
場における薬液貯槽。It has electrical properties, heat resistance, high adhesion, and good molding workability, and is also excellent in chemical resistance, especially oxidation resistance, so it is a chemical equipment material T1, especially reinforced with V& fiber such as glass fiber. Widely used as a matrix (base material) for corrosion-resistant W4 miscellaneous reinforced plastics (corrosion-resistant FRP), for example, in chemical storage tanks in chemical factories.
塔槽類、公害防止機器或いは配管等の材料にもかなり使
われている。しかしながらＦＲＰの用途拡大により、史
に高度の耐蝕性、耐熱性を備え、しかも室温作業性を兼
ね備えた樹脂が要求されるようになった。It is also widely used as a material for towers and tanks, pollution prevention equipment, piping, etc. However, as the use of FRP has expanded, there has been a demand for resins that have a high degree of corrosion resistance, heat resistance, and workability at room temperature.
（発明の目的） 本発明者はビニルエステル樹脂の優れた諸特性。(Purpose of the invention) The present inventor has discovered various excellent properties of vinyl ester resin.
特に低温作業性を何ら低下させることなく高度の耐熱性
を有する樹脂を得る目的で鋭意検討した結果、ノボラッ
ク型エポキシアクリレートを主成分としスチレンモノマ
ーとジビニルベンゼンを含むビニルエステル樹脂組成物
が、上記目的を充分達成し得ることを児出し本発明を完
成させるに至ったものである。In particular, as a result of intensive studies aimed at obtaining a resin with high heat resistance without any reduction in low-temperature workability, a vinyl ester resin composition containing novolak-type epoxy acrylate as a main component and styrene monomer and divinylbenzene was developed for the above purpose. The present invention has been completed by devising that the above can be fully achieved.
（発明の構成）
本発明は、
ａ）ノボラック型エポキシアクリレートを少くとも２０
重量％含むエポキシアクリレート類１００重量部。(Structure of the Invention) The present invention provides the following features: a) Novolac type epoxy acrylate at least 20%
100 parts by weight of epoxy acrylates containing % by weight.
ｂ）スチレンモノマー ５〜７０Φ足部。b) Styrene monomer 5-70Φ leg.
Ｃ）ジビニルベンゼン ２０〜９０重量部上記
ａ）、ｂ）及びＣ）を含むことを特徴とする耐熱性ビニ
ルエステル樹脂組成物を提供するものである。C) Divinylbenzene 20 to 90 parts by weight The present invention provides a heat-resistant vinyl ester resin composition characterized by containing the above a), b), and C).
本発明に用いるエポキシアクリレート類は、下記の一般
式（Ｉ＞
（但し、式中Ｒ１，Ｒ２は夫々独立に選ばれた一Ｆ＋、
−ＣＩ−１３、−Ｆ、 −Ｃ１ｌ、 −Ｂｒ又は−■
のいずれかひとつであり、ｎはＯ若しくは１〜１５の整
数である。）
で示されるノボラック型エポキシ樹脂をアクリル酸若し
くはメタクリル酸と反応させて得られるノボラック型エ
ポキシ（メタ）アクリレートを少くとも２０重量％とノ
ボラック型以外のエポキシ（メタ）アクリレートを含む
ものである。ノボラック型以外のエポキシアクリレート
としては、粘度が２５℃で１０００−２００００センヂ
ポイズの液状エポキシ樹脂を（メタ）アクリル酸と反応
させて得られるエポキシ（メタ）アクリレートが望まし
い。これらの例としては、下記の一般式（ｎ）
（但し、式中Ｒ３は−Ｈ又は−ＣＨ３であり、Ｒ４−Ｒ
７は夫々独立に−）（、ｌ、−α。The epoxy acrylates used in the present invention have the following general formula (I> (wherein R1 and R2 are each independently selected -F+,
-CI-13, -F, -C1l, -Br or -■
and n is O or an integer from 1 to 15. ) Contains at least 20% by weight of novolak-type epoxy (meth)acrylate obtained by reacting a novolak-type epoxy resin represented by the following with acrylic acid or methacrylic acid, and epoxy (meth)acrylate other than novolak-type. As the epoxy acrylate other than the novolak type, epoxy (meth)acrylate obtained by reacting a liquid epoxy resin with a viscosity of 1,000 to 20,000 centipoise at 25° C. with (meth)acrylic acid is desirable. Examples of these include the following general formula (n) (wherein R3 is -H or -CH3, and R4-R
7 are each independently −)(, l, −α.
−Ｂｒ又は−１より選ばれたいずれか一種である。-Br or -1.
Ａは
又は−〇−である。またｍは０若しくは１〜８の整数で
ある。）
で示されるビスフェノール型エポキシ樹脂をアクリル酸
若しくはメタクリル酸と反応させて得られるビスフェノ
ール型エポキシアクリレートの外、特殊エポキシ樹脂に
属する脂環族型、グリシジルエステル型、或いはヒダン
１〜イン型エポキシ樹脂等で粘度が２５°Ｃで１０００
〜２００００センチポイズである液状エポキシ樹脂を（
メタ）アクリル酸と反応さｌ！て得られるエポキシ（メ
タ）アクリレート等が挙げられる。特により優れた低温
作業性が要求される場合には液状ビスフェノール型エポ
キシ樹脂を（メタ）アクリル酸と反応さＵて１９られる
ビスラ１ノール型エポキシ（メタ）アクリレートを併Ｕ
て含有したものが好ましく用いられる。A is or -〇-. Moreover, m is 0 or an integer of 1 to 8. ) In addition to bisphenol-type epoxy acrylates obtained by reacting bisphenol-type epoxy resins shown in () with acrylic acid or methacrylic acid, alicyclic type, glycidyl ester type, or hydan-1-in type epoxy resins belonging to special epoxy resins, etc. The viscosity is 1000 at 25°C.
~20000 centipoise liquid epoxy resin (
meth) Reacts with acrylic acid! Examples include epoxy (meth)acrylates obtained by In particular, when better low-temperature workability is required, a liquid bisphenol-type epoxy resin can be reacted with (meth)acrylic acid and a bisla-1-nol type epoxy (meth)acrylate can be added.
Preferably, those containing
上記のエポキシ樹脂は一般に単一分子ｍの化合物として
よりも数種の異なる分子量をもった化合物の混合物とし
て使用されているのが現状であり、本発明においても分
子量分イ［の程度により制限されるものではない。At present, the above-mentioned epoxy resin is generally used as a mixture of several kinds of compounds with different molecular weights rather than as a compound with a single molecule m, and in the present invention, it is also limited by the degree of molecular weight. It's not something you can do.
本発明のエポキシアクリレート類は従来公知の製造方法
に従って容易に製造することができる。The epoxy acrylates of the present invention can be easily produced according to conventionally known production methods.
例えば、上記各種のエポキシ樹脂をスチレンモノマーに
加温溶解させ、これと当量の（メタ）アクリル酸をトリ
エチルアミン等の反応触媒、ハイドロキノン等の重合禁
止剤の存在下に反応さけるとエポキシアクリレート類が
得られ、次いでジビニルベンゼンを添加することにより
本発明の耐熱″１生ビニルニスデル樹脂組成物が１ｑら
れる。For example, epoxy acrylates can be obtained by heating and dissolving the various epoxy resins mentioned above in styrene monomer, and reacting the same amount of (meth)acrylic acid in the presence of a reaction catalyst such as triethylamine and a polymerization inhibitor such as hydroquinone. and then divinylbenzene is added to give 1q of the heat-resistant raw vinyl Nisder resin composition of the present invention.
本発明に用いるエポキシアクリレ−１・類は必須成分と
して２０重量％以上、望ましくは３０ｆｆｉ２％以上の
ノボラック型エポキシ（メタ）アクリレート８含ｆｉす
る。２０重量％未満では耐熱性が十分でない。より高度
の耐熱性を所望する場合には、ハロゲン化ノボラック型
エポキシ（メタ）アクリレ−１〜を用いるのがよい。The epoxy acrylate type 1 used in the present invention contains novolac type epoxy (meth)acrylate 8 as an essential component in an amount of 20% by weight or more, preferably 2% or more of 30ffi. If it is less than 20% by weight, heat resistance will not be sufficient. When higher heat resistance is desired, halogenated novolac type epoxy (meth)acrylates 1 to 1 are preferably used.
この場合スチレンモノマーを本発明の範囲内で多く用い
ることにより樹脂組成物の粘度を調整して作業性の向上
を図ることができる。またハロゲン化ノボラック型エポ
キシ（メタ）アクリレートとジビニルベンゼンの相乗効
果により高度の耐熱性を得ることができる。In this case, by using a large amount of styrene monomer within the range of the present invention, the viscosity of the resin composition can be adjusted and workability can be improved. Further, a high degree of heat resistance can be obtained due to the synergistic effect of the halogenated novolac type epoxy (meth)acrylate and divinylbenzene.
エポキシアクリレート類に所望により８０ｆｆｉｆｆｉ
％未満含まれるノボラック型以外のエポキシ（メタ）ア
クリレートは樹脂組成物の粘度を調整し作業性向上に寄
与することができる。80ffiffi for epoxy acrylates as desired
The epoxy (meth)acrylate other than the novolac type contained in an amount of less than % can adjust the viscosity of the resin composition and contribute to improving workability.
本発明のスチレンモノマーの使用量はエポキシアクリレ
ート類１００重量部当り５〜７０重量部、望ましくは８
〜５０重量部である。５重量部未満では樹脂組成物の粘
度が高くなり過ぎて作業性が低下し、７０重ｄ部を超え
る出では耐熱性が低下する。The amount of the styrene monomer used in the present invention is 5 to 70 parts by weight, preferably 8 parts by weight, per 100 parts by weight of the epoxy acrylate.
~50 parts by weight. If it is less than 5 parts by weight, the viscosity of the resin composition becomes too high and workability is reduced, and if it exceeds 70 parts by weight, heat resistance is reduced.
スチレンモノマーの添加はエポキシ樹脂の粘度に応じて
エポキシ樹脂を溶解する際或いはエポキシアクリレート
類の粘度を調整する際のいずれで・ｂ行うことができる
。The styrene monomer can be added depending on the viscosity of the epoxy resin either when dissolving the epoxy resin or when adjusting the viscosity of the epoxy acrylate.
ジビニルベンゼンの使用間はエポキシアクリレート類１
００重量部当り２０〜９０重間部、望ましくは３０〜８
０重量部である。２０重量部未満では樹脂の耐熱性が低
下し、９０重四部を超える量では樹脂組成物の粘度が高
くなり過ぎて作業性が著しく低下する。Epoxy acrylates 1 while using divinylbenzene
20 to 90 parts by weight per 00 parts by weight, preferably 30 to 8 parts by weight
It is 0 parts by weight. If the amount is less than 20 parts by weight, the heat resistance of the resin will decrease, and if the amount exceeds 90 parts by weight, the viscosity of the resin composition will become too high, resulting in a significant decrease in workability.
本発明に用いるノボラック型エポキシ（メタ）アクリレ
ートは従来耐熱性を有するものの粘度が高くなり過ぎて
作業性に劣るとされていたものであり、スチレンモノマ
ーを添加することによってその粘度調整は可能であるが
、耐熱性の大幅低下が免れ得なかったものである。本発
明においては特定量のジビニルベンゼンを併Ｕて添加す
ることにより耐熱性を落すことなしに樹脂組成物の粘度
を下げ、作業性の向上を図ることが可能となったもので
ある。またハロゲン化ノボラック型エポキシ（メタ）ア
クリレートをジビニルベンピンと併せて用いることによ
り、更に優れた作業性と高度の耐熱性を付与することが
できるばかりでなく、耐酸化性或いは耐薬品性をも向上
させることが可能となったものである。Although the novolac type epoxy (meth)acrylate used in the present invention has conventional heat resistance, it has been thought that the viscosity is too high and the workability is poor, but the viscosity can be adjusted by adding styrene monomer. However, a significant decrease in heat resistance could not be avoided. In the present invention, by adding a specific amount of divinylbenzene, it is possible to lower the viscosity of the resin composition without reducing heat resistance and improve workability. Furthermore, by using halogenated novolac type epoxy (meth)acrylate in combination with divinylbenpine, it is possible to not only provide even better workability and high heat resistance, but also improve oxidation resistance and chemical resistance. It is now possible to do so.
本発明の樹脂組成物にはビニルエステル樹脂に従来一般
に用いられているナフテン酸銅等の貯蔵安定剤或いはワ
ックス、シリコン等の添加剤を添加して差支えない。ま
た使用に際しては硬化剤。The resin composition of the present invention may contain storage stabilizers such as copper naphthenate or additives such as wax and silicone, which are commonly used in vinyl ester resins. Also a hardening agent when used.
充填剤、ｍ料、離型剤或いは補強材等必要に応じて配合
する。Fillers, additives, mold release agents, reinforcing materials, etc. are added as necessary.
本発明の耐熱性ビニルエステル樹脂組成物は従来のビニ
ルエステル樹脂と同様の硬化系によって室温で容易に硬
化さＩることができる。即ち本発明の樹脂組成物に有機
過酸化物、金属石けん及びアセト酢酸エステル若しくは
有機アミン化合物を添加し十分撹拌混合して硬化させる
。The heat-resistant vinyl ester resin composition of the present invention can be easily cured at room temperature using the same curing system as conventional vinyl ester resins. That is, an organic peroxide, a metal soap, and an acetoacetate or an organic amine compound are added to the resin composition of the present invention, and the mixture is sufficiently stirred and mixed to be cured.
硬化剤として用いられる右は過酸化物は室温にて通常使
用されているメヂルエチルケトンパーオキリイド等のり
°１−ンバーオキサイド、ベンゾイルパーＡキザイド等
のジアシルパーオキサイド或いはターシＶリーブチルバ
ーベンゾエイト等のパーオキシエステル等ビニルエステ
ル樹脂に用いられている硬化剤であればよく、特に制限
されるものではない。The peroxides on the right used as hardeners include adhesive resins such as methyl ethyl ketone peroxylide, diacyl peroxides such as benzoyl peroxyde, and diacyl peroxides such as benzoyl peroxyde, which are commonly used at room temperature. The curing agent may be any curing agent used for vinyl ester resins such as peroxy esters such as 8, and is not particularly limited.
金属石け／υは炭素数２〜１８個の有１１酸コバルト塩
が主に用いられるが、中でもオクデン酸］バルト、ナフ
テン酸コバルトが樹脂との相溶性の面から最も好ましく
用いられる。As the metal soap/υ, cobalt salts of 11 acids having 2 to 18 carbon atoms are mainly used, and among them, balt ocdenate and cobalt naphthenate are most preferably used from the viewpoint of compatibility with the resin.
アセト酢酸エステルは一般式
％式％
（但し式中Ｒは炭素数１〜６のアルキル基又はシクロア
ルキル基である。）
で示される化合物が用いられ、通常はアセト酢酸エチル
エステルが用いられる。As the acetoacetate, a compound represented by the general formula % (wherein R is an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms) is used, and ethyl acetoacetate is usually used.
有機アミン化合物はＮ、Ｎ−ジメチルアニリン。The organic amine compound is N,N-dimethylaniline.
Ｎ、Ｎ−ジエチルアニリン、 Ｎ、Ｎ−ジメチル１へ
ルイジン、 Ｎ、Ｎ−ジエチル（ヘルイジン、 Ｎ
、Ｎ−ビス（２−にドロキシエチル）アニリン、 Ｎ
、Ｎ−ビス（２−ヒト［１キシプロピル）トルイジン、
１−メチル−と３．／ｌ−４−リヒドロキノリン等の
芳香族アミン類或いはトリエチルアミン、トリブヂルア
ミン、Ｎ−メチルモルホリン、Ｎ−メヂルピベリジン、
１〜リエチレンジアミン等の３ｔｉ＆アルキルアミン類
が用いられる。N,N-diethylaniline, N,N-dimethyl 1heruidine, N,N-diethyl(heruidine, N
, N-bis(2-droxyethyl)aniline, N
, N-bis(2-human[1xypropyl)toluidine,
1-methyl- and 3. Aromatic amines such as /l-4-lihydroquinoline, triethylamine, tribudylamine, N-methylmorpholine, N-medylpiverdine,
1 to 3ti&alkylamines such as lyethylenediamine are used.
また耐熱性の優れた低温硬化系としてアセト酢酸ニスデ
ルパーオキサイド、６機コバルト塩及びアセト酢酸エス
テルの組合せ（特公昭５７−４２０８７１号参照。）や
精製メチルエチルケトンパーオキサイド、第３級アルキ
ルパーオキシエステル、有機コバルト塩、アセト酢酸エ
ステルの組合しく特公昭５７−４２８５号参照。）等が
開示されておりこれらも用いることができる。尚、従来
ビニルエステル樹脂の低温硬化後硬化をより完全にする
際アフターキュアーが行われているが、本発明の組成物
にλ１しても６０″ＣＪ：ｌＪ−の温度でアノクーキュ
アーすることができる。In addition, as a low-temperature curing system with excellent heat resistance, a combination of acetoacetate nysdel peroxide, hexagonal cobalt salt, and acetoacetate ester (see Japanese Patent Publication No. 57-420871), purified methyl ethyl ketone peroxide, and tertiary alkyl peroxy ester , organic cobalt salt, and acetoacetic ester, see Japanese Patent Publication No. 57-4285. ) etc. are disclosed and these can also be used. Although after-curing is conventionally performed to further complete curing after low-temperature curing of vinyl ester resins, the composition of the present invention may be anodically cured at a temperature of 60"CJ:lJ- even at λ1. I can do it.
本発明の樹脂組成物には補強材として通常用いられるカ
ラス載着［がストランド、チョップトスＩヘランド、ヂ
ョツブドス１〜ランドマット、サーフェスマット、ロー
ヒング、ロービングクロス、クロスデープ或いはスワー
ルマット等種々の形態で用いられ、ＦＲＰの用途及び成
形法に応じて適宜選択される。また上記ガラス繊維の外
にカーボン繊維、有機質、ｍｍ等を必要に応じて併用す
ることができる。The resin composition of the present invention can be used in various forms such as strands, chopped roving cloth, roving cloth, cross-deep mats, swirl mats, etc., which are commonly used as reinforcing materials. , is appropriately selected depending on the use of FRP and the molding method. Further, in addition to the above-mentioned glass fibers, carbon fibers, organic materials, mm, etc. can be used in combination as necessary.
成形方法は従来ＦＲＰの成形法として知られている方法
でよく、例えばハンドレイアップ法、スプレーアップ法
、フィラメン１〜ワインディング法。The molding method may be a method conventionally known as a molding method for FRP, such as a hand lay-up method, a spray-up method, or a filament 1-winding method.
遠心成形法或いはレジンインジェクション法等いずれの
方法でも用いられる。Any method such as a centrifugal molding method or a resin injection method can be used.
通常ＦＲＰ加工においてガラス繊Ｉｆｔ等の繊維に樹脂
組成物を含浸さぜ脱泡する等の作業工程に最適な樹脂粘
度は室温で２００〜５００センチポイズという比較的狭
い範囲にあって、この範囲を逸脱すると作業性が著しく
損われ、更にはＦＲＰの所期の特性が損われるのである
が、本発明の樹脂組成物は作業性を損わない粘度範囲を
維持し且つ通常の加工作業、更には小ざな曲率半径を有
りる成を作業も行うことができ、しかもその硬化物は耐
熱性を従来のものより数十℃向上させた優れたものが１
７られる。Normally, in FRP processing, the optimal resin viscosity for work processes such as impregnating fibers such as glass fiber Ift with a resin composition and defoaming is within a relatively narrow range of 200 to 500 centipoise at room temperature, and deviates from this range. This significantly impairs workability and further impairs the intended properties of FRP, but the resin composition of the present invention maintains a viscosity range that does not impair workability and can be used in normal processing operations and even small-scale processing operations. It is possible to work on materials with a rough radius of curvature, and the cured product has excellent heat resistance that is several tens of degrees higher than conventional products.
7.
（発明の効果）
本発明の耐熱性ビニルエステル樹脂組成物はノボラック
型エポキシ（メタ）アクリレートを主成分とし要すれば
ビスフェノール型エポキシ（メタ）アクリレート等の他
種のエポキシ（メタ）アクリレ−１〜の外にスチレンモ
ノマー及びジビニルベンピンを併せて含（ｊする樹脂組
成物であって、ガラス繊維に対する含浸性や脱泡性’６
Ｆ ＲＰの作業性を低下させることなしに、室温にて
硬化させるという従来の方法を何ら変更することがなく
、硬化物の耐熱性を従来よりも大幅に向上させたもので
あり、中でもハロゲン化ノボラック型１ボキシ（メタ）
アクリレートとジビニルベンゼンを併用することにより
耐熱ｔ’を及び作業性の箸しく優れたちのが１７られ、
工業材料としてその適用範囲を著しく拡大することが出
来る・ｂのである。(Effects of the Invention) The heat-resistant vinyl ester resin composition of the present invention contains novolac type epoxy (meth)acrylate as a main component, and if necessary, other types of epoxy (meth)acrylates such as bisphenol type epoxy (meth)acrylate. A resin composition containing styrene monomer and divinylbenpine in addition to
This method significantly improves the heat resistance of the cured product compared to the conventional method without reducing the workability of FRP and without changing the conventional method of curing at room temperature. Novolak type 1 boxy (meth)
By using acrylate and divinylbenzene together, heat resistance t' and workability are excellent.
As an industrial material, its range of application can be significantly expanded.
以下実施例により本発明を更に具体的に詳細説明づる。The present invention will be explained in more concrete detail with reference to Examples below.
尚例中の部は小量基準である。Note that the parts in the examples are based on small quantities.
実施例１
撹拌機、冷却器、加熱装置及び温度泪を漏えた四つロフ
ラスコにエポキシ当量２１４の０−タレゾールノボラッ
ク型エポキシ樹脂（東部化成社製「エポトー１〜ＹＤＣ
ＩＩ−７０３Ｊ ） ２２９部、エポキシ当量１８５
のビスフェノール型エポキシ樹脂（油化シェルエポキシ
社製［エピコート８２８Ｊ ） ／１５７部を仕込み
スチレンモノマー８６部を加えて８０〜９０℃にて溶解
する。これにメタクリル酸３０５部、ハイドロキノン０
．３部及び１〜リ工チルアミン９部を１１０℃にて約４
０分間で添加し、同温度にて１５０分間反応させ、酸価
が９に達したところで反応を終了し、次いでジビニルベ
ンビン（三共化成礼装）４９０部を添加して耐熱性ビニ
ルニスデル樹脂組成物を１−Ｉだ。（エポキシアクリレ
ート類中ノボラッり型３２％含右含有この組成物の外観
は透明な褐色の液体であり、Ｂ型粘度計によるその粘度
は２５℃で３１０センヂポイズであった。Example 1 A 0-talesol novolac type epoxy resin (manufactured by Tobu Kasei Co., Ltd. "Epoto 1~YDC") with an epoxy equivalent of 214 was placed in a four-bottle flask containing a stirrer, a cooler, a heating device, and a temperature drop.
II-703J) 229 parts, epoxy equivalent weight 185
157 parts of bisphenol type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd. [Epicoat 828J)] was charged, 86 parts of styrene monomer was added, and the mixture was dissolved at 80 to 90°C. This includes 305 parts of methacrylic acid and 0 parts of hydroquinone.
．． 3 parts and 1 to 9 parts of re-engineered tylamine at 110°C to approx.
The reaction was carried out for 150 minutes at the same temperature, and the reaction was terminated when the acid value reached 9. Then, 490 parts of divinylbenvin (Sankyo Kasei-So) was added to prepare a heat-resistant vinyl Nisder resin composition. It's 1-I. (Containing 32% novolatile type among epoxy acrylates) The appearance of this composition was a transparent brown liquid, and its viscosity measured by a B-type viscometer was 310 centipoise at 25°C.
この組成物を用いて以下の方法で樹脂注型板を作製した
。前記耐熱性ビニルニスデル樹脂組成物の１ボキシアク
リレ一ト類１００部に対して表１に示した如く硬化剤Ａ
（生薬ヌーり社製［硬化剤３２８Ｊ ） ２．０部、
ナフテン酸］バルト（金属含有ｍ６％、以下同じ。）０
．５部及びアセト酢酸エヂルエスデル０．２部を添加し
充分撹拌させて樹脂液を１また。A resin cast plate was produced using this composition in the following manner. Curing agent A as shown in Table 1 was added to 100 parts of the 1-boxyacrylate of the heat-resistant vinyl Nisder resin composition.
(manufactured by Herbal Medicine Nouri Co., Ltd. [hardening agent 328J) 2.0 parts,
Naphthenic acid] Balt (metal content m6%, same hereinafter) 0
．． 5 parts of acetoacetate and 0.2 parts of edyl ester acetoacetate were added, and the resin solution was mixed by stirring thoroughly.
２００ｘ ２００ｘ厚ざ３ｍｍの２枚のガラス板の内面
を固形ワックス（公道ケミカル社製「ボンリースト１」
）にて３回離型処理し、厚さ１０ｍｍのシリコーンゴム
枠をスペーリーーとして上記２枚のガラス板で挟みクリ
ップでクランプした。この１０１１１１１１のガラス板
の隙間に上記樹脂液を注入し、室温にて約１時間保持し
た。硬化発熱したものを冷却後ガラス板の間から注型板
を取り出した。この注型板は均質且つ透明でその表面の
硬さはバーコル硬麻計（バーバー］−ルマン社製ｒＧＹ
ＺＪ ９３４− ＩＪ使川用Ｊ Ｉ Ｓ Ｋ６９１９に
拠る。）により５０であった。The inner surfaces of two glass plates measuring 200 x 200 x 3 mm in thickness were coated with solid wax (“Bonreest 1” manufactured by Kodo Chemical Co., Ltd.).
), and the silicone rubber frame with a thickness of 10 mm was used as a spacer and was sandwiched between the two glass plates and clamped with a clip. The resin liquid was injected into the gap between the 10111111 glass plates and kept at room temperature for about 1 hour. After cooling the material that generated heat during curing, the casting plate was taken out from between the glass plates. This casting plate is homogeneous and transparent, and its surface hardness is determined by the Barcol Hardness Tester (Barbour) - rGY manufactured by Le Mans.
ZJ 934- Based on JIS K6919 for IJ Shikawa. ) was 50.
これに続＜ｔＴ １００”Ｏｘ １時間、 １５０’
Ｃｘ １時間及び２００℃×２時間のアフターキュアを
施した後、バーコル硬ざ及び熱変形温度（東洋精機社製
［熱変形温度測定機１１ＤＴ＆ ＶＳＰＴ Ｔｅ５ｔｅ
ｒＪ使用、ＪＩＳＫ６９１９に拠る。）を測定した結果
は表１に示した通りであった。Following this <tT 100"Ox 1 hour, 150'
After curing for 1 hour and after-curing at 200°C for 2 hours, the Barcol hardness and heat distortion temperature (manufactured by Toyo Seiki Co., Ltd. [Heat distortion temperature measurement device 11DT & VSPT Te5te]
rJ used, based on JISK6919. ) The results of the measurements were as shown in Table 1.
実施例２〜４
前記実施例１と同様にして、エポキシ当ｌ ２８０の臭
素化ノボラック型エポキシ樹脂（日本生薬社製ｒＢＲＥ
Ｎ−３Ｊ ）７５４部にスチレンモノマーを夫々実施例
２は３００部、実施例３は３９０部、実施例４は４８０
部添加し８５〜９５℃にで溶解する。これにメタクリル
酸２３１部、ハイドロキノン０．２部及びトリエチルア
ミン１５部を１１０℃にて約４５分間で添加し、同温度
にて１３５分間反応させ、酸価が８に達したところで反
応を終了し、次いでジビニルベンゼンを夫々３５０部添
加して耐熱性ビニルエステル樹脂組成物を冑た。このも
のの外観は透明な褐色の液体であった。この組成物に表
１に示した硬化系試薬を添加し実施例１と同様にして作
製した注型板につき試験した結果を表１に併Ｕて示した
。Examples 2 to 4 In the same manner as in Example 1, a brominated novolac type epoxy resin (rBRE manufactured by Nippon Koyaku Co., Ltd.) with an epoxy weight of 280
N-3J) 754 parts of styrene monomer, respectively in Example 2, 300 parts, Example 3, 390 parts, and Example 4, 480 parts.
% and dissolve at 85-95°C. To this, 231 parts of methacrylic acid, 0.2 parts of hydroquinone, and 15 parts of triethylamine were added at 110°C for about 45 minutes, and the reaction was allowed to proceed at the same temperature for 135 minutes, and the reaction was terminated when the acid value reached 8. Next, 350 parts of divinylbenzene was added to each to dissolve the heat-resistant vinyl ester resin composition. The appearance of this substance was a transparent brown liquid. Table 1 also shows the results of tests on casting plates prepared in the same manner as in Example 1 by adding the curing reagents shown in Table 1 to this composition.
実施例５〜７
前記実施例１と同様にして、Ｏ−クレゾールノボラック
型■ボキシ樹脂（実施例１と同じ。）１２６部、臭素化
ノボラック型■ボキシ樹脂（実施例２と同じ。）３３６
部及びビスラエノール型エポキシ樹脂（実施例１と同じ
。）２５２部にスチレンモノマーを夫々実施例５は４７
０部、実施例６は４００部、実施例７は３００部添加し
８５〜９５℃にて溶解゛する。これにメタクリル酸２７
３部、ハイドロキノン０．２部及びトリエチルアミン１
３部を１１０℃にて約４０分間で添加し、同温度にて１
５０分間反応させ、酸価が９に達したところで反応を終
了し、次いでジビニルベンピンを夫々実施例５は５３ｏ
６Ｂ。Examples 5 to 7 In the same manner as in Example 1, 126 parts of O-cresol novolak type ■boxy resin (same as in Example 1) and 336 parts of brominated novolak type ■boxy resin (same as in Example 2) were added.
In Example 5, styrene monomer was added to 252 parts and 252 parts of bisthraenol type epoxy resin (same as in Example 1).
0 parts, 400 parts for Example 6, and 300 parts for Example 7 and melted at 85-95°C. In this, methacrylic acid 27
3 parts, 0.2 parts of hydroquinone and 1 part of triethylamine
3 parts were added in about 40 minutes at 110°C, and 1 part was added at the same temperature.
The reaction was carried out for 50 minutes, and the reaction was terminated when the acid value reached 9. Then, divinylbenpine was added to 53o
6B.
実施例６は６００部、実施例７は７００部添加して耐熱
性ビニルエステル樹脂組成物を得た。（いずれもエポキ
シアクリレート類中ノボラック型６３％含有。）このも
のの外観は透明な褐色の液体であった。この組成物に表
１に示した硬化系試薬を添加し実施例１と同様にして試
験した結果を表１に（Ｊｆぜて示した。A heat-resistant vinyl ester resin composition was obtained by adding 600 parts for Example 6 and 700 parts for Example 7. (Both contained 63% novolac type among epoxy acrylates.) The appearance of this product was a transparent brown liquid. The curing reagents shown in Table 1 were added to this composition and tested in the same manner as in Example 1. The results are shown in Table 1 (Jf).
比較例１，２
表２に示したスチレンモノマー及びジビニルベンピンを
用いた以外は実施例１と同様にして樹脂組成物を調製し
、試験した結果を表２に併セて示しｌこ。Comparative Examples 1 and 2 A resin composition was prepared in the same manner as in Example 1 except that the styrene monomer and divinylbenpine shown in Table 2 were used, and the test results are also shown in Table 2.
比較例３，４
表２に示したスチレンモノマー及びジビニルベンゼンを
用いた以外は実施例３．４と同様にして樹脂組成物を調
製し、試験した結果を表２にｖｌせて示した。Comparative Examples 3 and 4 A resin composition was prepared in the same manner as in Example 3.4 except that the styrene monomer and divinylbenzene shown in Table 2 were used, and the test results are shown in Table 2.
比較例５．６
表２に示したスチレンモノマー及びジビニルベンゼンを
用いた以外は夫々実施例５．６と同様にして樹脂組成物
を調製し、試験した結果を表２に併μで示した。Comparative Example 5.6 Resin compositions were prepared in the same manner as in Example 5.6 except that the styrene monomer and divinylbenzene shown in Table 2 were used, and the test results are shown in Table 2 in μ.
Claims (1)
重量％含むエポキシアクリレート類１００重量部、 ｂ）スチレンモノマー５〜７０重量部。 ｃ）ジビニルベンゼン２０〜９０重量部 上記ａ）、ｂ）及びｃ）を含むことを特徴とする耐熱性
ビニルエステル樹脂組成物。[Claims] a) at least 20 novolak-type epoxy acrylates;
b) 5 to 70 parts by weight of styrene monomer. c) 20 to 90 parts by weight of divinylbenzene A heat-resistant vinyl ester resin composition comprising the above a), b) and c).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9533288A JPH01266120A (en) | 1988-04-18 | 1988-04-18 | Heat-resistant vinyl ester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9533288A JPH01266120A (en) | 1988-04-18 | 1988-04-18 | Heat-resistant vinyl ester resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01266120A true JPH01266120A (en) | 1989-10-24 |
Family
ID=14134764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9533288A Pending JPH01266120A (en) | 1988-04-18 | 1988-04-18 | Heat-resistant vinyl ester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01266120A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62106916A (en) * | 1985-11-05 | 1987-05-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Resin composition which can give cured product of excellent heat stability |
-
1988
- 1988-04-18 JP JP9533288A patent/JPH01266120A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62106916A (en) * | 1985-11-05 | 1987-05-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Resin composition which can give cured product of excellent heat stability |
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