JPS6231020B2 - - Google Patents
Info
- Publication number
- JPS6231020B2 JPS6231020B2 JP14654979A JP14654979A JPS6231020B2 JP S6231020 B2 JPS6231020 B2 JP S6231020B2 JP 14654979 A JP14654979 A JP 14654979A JP 14654979 A JP14654979 A JP 14654979A JP S6231020 B2 JPS6231020 B2 JP S6231020B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- coumaron
- modified
- resins
- weight
- 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
Links
- 229920005989 resin Polymers 0.000 claims description 111
- 239000011347 resin Substances 0.000 claims description 111
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 87
- 239000003822 epoxy resin Substances 0.000 claims description 58
- 229920000647 polyepoxide Polymers 0.000 claims description 58
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 239000003208 petroleum Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 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 26
- 239000003921 oil Substances 0.000 description 18
- 239000003973 paint Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 238000009835 boiling Methods 0.000 description 2
- 150000001907 coumarones Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 naphthenic Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は新規なる変性クマロン樹脂とクマロン
樹脂及び／又は石油樹脂との混合変性クマロン樹
脂をエポキシ樹脂に配合した樹脂組成物に関す
る。更に詳しくはクマロン樹脂製造用原料油より
変性クマロン樹脂を製造し、これに従来のクマロ
ン樹脂及び／又は石油樹脂を配合し、この混合樹
脂をエポキシ樹脂に配合することによりエポキシ
樹脂の防食性を向上させ、増量させた樹脂組成物
に関する。従来からクマロン樹脂或は石油樹脂は
ホワイトタールの名称により、エポキシ樹脂の増
量材或はタールエポキシ樹脂のタール成分の代替
として着色塗料又は重防食塗料に使用されてい
る。
しかしながら上記の塗料用として使用する、エ
ポキシ樹脂は低分子量樹脂であれば該クマロン樹
脂或は石油樹脂と相溶するが、高分子量のエポキ
シ樹脂では相溶性が悪く、この傾向はエポキシ樹
脂の分子量が大きくなればなる程、ますます相溶
性は悪くなる傾向にある。
相溶性が悪いということは両樹脂が無理に混ぜ
られているために両者を混合した場合、分離し、
塗料膜を作成した場合、該乾燥塗膜が白濁するた
め、外観上、ツヤ消し状態もしくは不鮮明な塗膜
しか形成されないのである。従つてクマロン樹脂
或は石油樹脂をエポキシ樹脂と共に使用する場合
には、必然的に低分子量のエポキシ樹脂しか採用
されずその使用量も制限されるため塗料配合にも
制限を受けることになる。
この様に従来のクマロン樹脂或は石油樹脂とエ
ポキシ樹脂とは相溶性が悪いので、前述の如く、
もともと無理に混ぜて使用するため、一見相溶性
が良い様に見えても塗膜にした場合、塗膜のチヨ
ーキングが早期に開始され、それにより塗膜の劣
化が促進される。
本発明者等はかかる事情に鑑み、上記の欠点を
解消するため、鋭意研究した結果、高分子量のエ
ポキシ樹脂とも充分に相溶性を有する混合変性ク
マロン樹脂を製出し、これをエポキシ樹脂に配合
した変性クマロン樹脂エポキシ樹脂組成物を発明
するに到つたのである。
これにより従来公知のクマロン樹脂或は石油樹
脂では利用出来なかつた高分子量エポキシ樹脂の
範囲まで使用することが可能となり、クマロン樹
脂としてはその応用範囲を拡大したものである。
本発明の混合変性クマロン樹脂は従来のクマロン
樹脂或は石油樹脂よりも極性基が導入されている
ため、相溶性に富むものであり、従来のクマロン
樹脂の応用分野を拡大するとき何ら縮少するもの
ではない。
すなわち、本発明はコークス炉ガス軽油、ター
ル軽油からのクマロン樹脂製造原料油を原料と
し、無機酸、有機酸、或はフリーデルクラフツ型
触媒を用い、ホルムアルデヒド類例えばホルマリ
ン、パラホルムアルデヒド等を変性剤として該原
料油100重量部に対して10〜80重量部を反応系内
に存在せしめて、本発明に使用する変性クマロン
樹脂を製造する。
そして該変性クマロン樹脂に対し、従来公知の
クマロン樹脂及び／又は石油樹脂を配合し、この
混合変性クマロン樹脂中の変性クマロン樹脂を50
〜90重量％として混合変性クマロン樹脂を製造す
る。この混合変性クマロン樹脂を、エポキシ樹脂
を100重量部とした場合その中の変性クマロン樹
脂が５〜400重量部となるように配合して出来た
変性クマロン樹脂エポキシ樹脂組成物が本発明で
ある。
ここでエポキシ樹脂の低分子量及び高分子量と
の境界を汎用のビスフエノールＡ型エポキシ樹脂
で説明する。エポキシ樹脂には周知の如く常温で
液状及び固形のものがあり、その分子量により状
態が変化する。
本発明において、その境界をエポキシ樹脂とし
て分子量900以下のものを低分子量エポキシ樹脂
とし、分子量900以上のものを高分子量エポキシ
樹脂と区別する。
本発明で使用する混合変性クマロン樹脂組成物
は低分子量エポキシ樹脂は勿論のこと、高分子量
エポキシ樹脂にも配合可能であり、そのエポキシ
樹脂との組成物は、従来のクマロン樹脂をエポキ
シ樹脂に配合したものより積層物にした場合、透
明性に優れ、塗料膜にした場合も耐食性、耐候性
に優れた硬化物となる。
変性クマロン樹脂に対し、従来公知のクマロン
樹脂及び／又は石油樹脂を配合するのは、変性ク
マロン樹脂は分子中に極性基が導入されるため、
エポキシ樹脂との相溶性がでて来るが、同時に、
このために耐食性と耐候性が、本来のクマロン樹
脂にくらべて劣つてくる。クマロン樹脂及び／又
は石油樹脂を配合することにより、この耐食性と
耐候性が改善される。本来変性クマロン樹脂製造
工程でホルムアルデヒド類の配合量を調節しても
改善されるが、この段階では原料油中の重合成分
の量とインデン、クマロン、スチレンの割合の変
動があり、触媒量温度等による重合度の変動もあ
り、当然エポキシ樹脂との相溶性が充分確保され
る様にホルムアルデヒド類も添加される。従つて
エポキシ樹脂との配合に当つては当然、相溶性が
確保される範囲で、耐食性と耐候性が確保される
様に通常のクマロン樹脂及び／又は石油樹脂を配
合するものである。又変性クマロン樹脂は、ホル
ムアルデヒド類の配合により当然コストも通常の
クマロン樹脂より高価になる。従つてエポキシ樹
脂に変性クマロン樹脂だけを配合するより混合変
性クマロン樹脂を配合すれば当然コスト削減にな
る。石油樹脂は分解ナフサ中の不飽和炭化水素を
重合させたもので、スチレン、インデンを主成分
とする、従つてクマロンを含まないという差異は
あるが、クマロン樹脂と成分的にも、物性的にも
類似した樹脂である。
次に本発明を詳述する。
本発明において使用する変性クマロン樹脂の製
造には、従来クマロン樹脂の製造に用いられる原
料油を使用する、すなわち、コークス炉、ガス軽
油、タール軽油の沸点範囲110〜210℃のスチレ
ン、クマロン、インデン、及びそれ等の誘導体で
あるC8〜C11留分を主成分とし、その他芳香族、
パラフイン、ナフテン系、炭化水素油を含む留分
を原料油として使用する。好ましくは原料油を処
理して130〜200℃の留分である。
このクマロン樹脂製造用原料油100重量部に対
して、ホルムアルデヒド類が10重量部より少ない
変性クマロン樹脂よりの組成物では低分子量のエ
ポキシ樹脂とは、ある程度相容するが、高分子量
エポキシ樹脂とは相容しない。ホルムアルデヒド
類を80重量部より多く使用した変性クマロン樹脂
を用いた組成物も作ることは可能であるが、従来
のクマロン樹脂の特性が失なわれる。
本発明に使用する変性クマロン樹脂の製造に使
用する触媒としては、硫酸、リン酸等の無機酸、
パラトルエンスルフオン酸等の有機酸又はフリー
デルクラフツ型触媒等が使用出来る。いづれもそ
れ等の単独或は２種類以上混合して使用すること
も出来る。その使用量は触媒の種類によつても異
なるが、原料油100重量部に対して0.1〜40重量％
であれば良い。いづれも触媒の種類等により最適
の組み合せを求めればよい。重合方法は一般の方
法でよく原料を還流冷却器付の反応釜に仕込み、
撹拌しながら０℃〜150℃で約30分〜10時間の反
応で本発明に使用する変性クマロン樹脂を製造し
得る。
すなわち本発明の組成物に使用する変性クマロ
ン樹脂とは従来クマロン樹脂の製造に用いられて
いた原料油をホルム―アルデヒド類で変性する変
性クマロン樹脂である。
本発明においては、この変性クマロン樹脂を従
来からのクマロン樹脂及び／又は石油樹脂に配合
し、この混合変性クマロン樹脂中の変性クマロン
樹脂を50〜90重量％とするように配合する。変性
クマロン樹脂がこの混合樹脂50重量％未満となる
と、エポキシ樹脂との相溶性が低下してくる。
変性クマロン樹脂の割合が多くなると、相溶性
はますますよくなる方向であるが、前記したよう
に通常のクマロン樹脂及び／又は石油樹脂が減少
することになるので90重量％より多くなると、耐
食性、耐候性が劣化し、混合変性クマロン樹脂と
してコストも高くなる。従つて50〜60重量％が好
ましい配合割合である。この混合変性クマロン樹
脂は、従来のクマロン樹脂では相溶性が悪いとさ
れていた高分子量のエポキシ樹脂との相溶性に優
れるものである。
ここで言う低分子量のエポキシ樹脂の例に、エ
ピコート827，828，834，871，872等（以上シエ
ル化学）、アラルダイトGY257，252，255，280等
（以上日本チバガイギー）、スミエポキシELA―
115，128等（以上住友化学）の汎用樹脂があり、
これ等はいずれも分子量が900以下で液状型エポ
キシ樹脂とも称せられるものである。また、それ
等のエポキシ樹脂を多価アルコール類或はアルカ
ノールアミン類等の反応によつて得られるポリオ
ール化された変性樹脂も本発明においてはこの範
疇に入るものとする。
高分子量エポキシ樹脂の例としてエピコート
1001，1004，1007，1009等（以上シエル化学）、
アラルダイト6071，7071，6084，7097，6097等
（以上日本チバガイギー）、スミエポキシESA―
011，014等（以上住友化学）等の汎用樹脂があ
り、これ等の樹脂の分子量はいずれも900以上の
ものであり、固形エポキシ樹脂とも称せられてい
る。また、それ等のエポキシ樹脂と多価アルコー
ル類或はアルカノールアミン類等の反応によつて
得られるポリオール化された変性樹脂も本発明に
おいてはこの範疇に入るものとする。その他、ノ
ボラツク型エポキシ樹脂或は、難燃化エポキシ樹
脂等の特殊骨格を有するエポキシ樹脂もあるが、
いずれも本発明においてはエポキシ樹脂としての
分子量900を境にして低分子量エポキシ樹脂と高
分子量エポキシ樹脂とに区別する。
これ等のエポキシ樹脂100部と配合する変性ク
マロン樹脂の量は５〜400重量部で好ましくは50
〜200重量部である。５重量％より少ない場合は
変性クマロン樹脂組成物としての効果に乏しく、
400重量％以上配合することも可能であるが、エ
ポキシ樹脂本来の性質を損う傾向にある。
本発明における混合変性クマロン樹脂組成物を
配合したエポキシ樹脂硬化物、例えば積層物、注
型品、或は塗料膜にした場合、従来のクマロン樹
脂、或は石油樹脂を配合したものよりはるかに透
明性にすぐれたものが提供し得る。
本発明における相溶性の試験方法は試験管にエ
ポキシ樹脂と本発明において製造した混合樹脂と
を１：１（重量比）で混合し、加熱溶融した後、
室温まで冷却してからその濁りの状態を観察す
る。
以下本発明を実施例を用いて説明する。本発明
で使用する変性クマロン樹脂の製造方法を参考例
として次に示す。
参考例
本発明に使用する変性クマロン樹脂の製造法(1)
石炭系のガス軽油、タール軽油を蒸留し、沸点
135℃〜195℃留分を採取しこれを重合原料油とし
た。１４つ口フラスコに37％ホルマリン250
ｇ、98％硫酸50ｇ、水100ｇを入れ70〜90℃に加
熱し、上記の重合原料油300ｇを滴下し90〜100℃
で１時間反応させた。反応終了後、反応生成物を
中和、洗浄処理して触媒を除去した後、未反応留
分を除き液状樹脂189ｇを得た。
本発明に使用する変性クマロン樹脂の製造法(2)
95％パラホルムアルデヒド100ｇ、重合原料油
300ｇを混合し撹拌する。30℃〜40℃に温度を維
持し、BF3―エチルエーテル錯塩7.0ｇを12分か
けて滴下した。滴下終了後、90〜100℃で4.5時間
反応させた。反応終了後、触媒除去、洗浄を行い
未反応分留分を除き、固形樹脂171ｇを得た。
本発明の組成物に使用する石油樹脂とは石油の
スチームクラツキングによつて得られる分解ナフ
サ中に存在する不飽和炭化水素を通常の触媒を用
いて重合したもので、一般に市販されているもの
で良く何ら制限を受けるものではない。
第１表は本発明における混合変性クマロン樹脂
とエポキシ樹脂とを配合した実施例と比較例を示
したものである。これらの配合物に従来から公知
のエポキシ樹脂の硬化剤を用いて硬化組成物とす
る。
The present invention relates to a resin composition in which a mixed modified coumaron resin, which is a mixture of a novel modified coumaron resin, a coumaron resin, and/or a petroleum resin, is blended with an epoxy resin. More specifically, a modified coumaron resin is produced from the raw material oil for producing coumaron resin, a conventional coumaron resin and/or petroleum resin is blended with this, and this mixed resin is blended with an epoxy resin to improve the corrosion resistance of the epoxy resin. The present invention relates to a resin composition whose amount has been increased. Conventionally, coumaron resin or petroleum resin has been used under the name of white tar in colored paints or heavy anticorrosive paints as an extender for epoxy resins or as a substitute for the tar component of tar epoxy resins. However, if the epoxy resin used for the above-mentioned paint is a low molecular weight resin, it is compatible with the Cumaron resin or petroleum resin, but a high molecular weight epoxy resin has poor compatibility, and this tendency is due to the molecular weight of the epoxy resin. The larger the size, the worse the compatibility tends to be. Poor compatibility means that both resins are forced to mix, so when they are mixed, they separate and
When a paint film is created, the dried paint film becomes cloudy, so that only a matte or indistinct paint film is formed in terms of appearance. Therefore, when a coumaron resin or a petroleum resin is used together with an epoxy resin, only a low molecular weight epoxy resin is necessarily used, and the amount used is also limited, which imposes restrictions on the formulation of the paint. In this way, conventional coumaron resin or petroleum resin and epoxy resin have poor compatibility, so as mentioned above,
Since they are mixed forcibly in the first place, even if they appear to be compatible at first glance, when they are made into a paint film, the paint film begins to choke early, which accelerates the deterioration of the paint film. In view of the above circumstances, in order to eliminate the above-mentioned drawbacks, the present inventors conducted intensive research and produced a mixed modified coumaron resin that is sufficiently compatible with high molecular weight epoxy resins, and blended this into epoxy resins. This led to the invention of a modified coumaron resin epoxy resin composition. This makes it possible to use a range of high molecular weight epoxy resins that could not be used with conventionally known coumaron resins or petroleum resins, thus expanding the range of applications of coumaron resins.
Since the mixed modified coumaron resin of the present invention has more polar groups introduced than conventional coumaron resins or petroleum resins, it is highly compatible, and when expanding the application fields of conventional coumaron resins, it will not be reduced in any way. It's not a thing. That is, the present invention uses coumaron resin production raw material oil from coke oven gas light oil or tar light oil as a raw material, uses an inorganic acid, an organic acid, or a Friedel-Crafts type catalyst, and modifies formaldehyde such as formalin, paraformaldehyde, etc. The modified coumaron resin used in the present invention is produced by allowing 10 to 80 parts by weight of the compound to be present in the reaction system based on 100 parts by weight of the raw material oil. Then, a conventionally known coumaron resin and/or petroleum resin is blended with the modified coumaron resin, and the modified coumaron resin in this mixed modified coumaron resin is
Produce mixed modified coumaron resin as ~90% by weight. The present invention is a modified coumaron resin epoxy resin composition prepared by blending this mixed modified coumaron resin in such a manner that the modified coumaron resin is in the range of 5 to 400 parts by weight when the epoxy resin is 100 parts by weight. Here, the boundary between low molecular weight and high molecular weight epoxy resins will be explained using a general-purpose bisphenol A type epoxy resin. As is well known, epoxy resins can be liquid or solid at room temperature, and their state changes depending on their molecular weight. In the present invention, the boundary is defined as an epoxy resin, and those with a molecular weight of 900 or less are classified as low molecular weight epoxy resins, and those with a molecular weight of 900 or more are distinguished from high molecular weight epoxy resins. The mixed modified coumaron resin composition used in the present invention can be blended not only with low molecular weight epoxy resins but also with high molecular weight epoxy resins, and the composition with the epoxy resin is a mixture of conventional coumaron resins with epoxy resins. When made into a laminate, it has excellent transparency, and when made into a paint film, it becomes a cured product with excellent corrosion resistance and weather resistance. The reason why conventionally known coumaron resins and/or petroleum resins are blended with modified coumaron resins is that modified coumaron resins have polar groups introduced into their molecules.
It becomes compatible with epoxy resin, but at the same time,
For this reason, its corrosion resistance and weather resistance are inferior to the original Cumaron resin. By blending coumaron resin and/or petroleum resin, this corrosion resistance and weather resistance are improved. Normally, it can be improved by adjusting the amount of formaldehyde compounded in the modified coumaron resin manufacturing process, but at this stage, the amount of polymerization components in the raw oil and the proportions of indene, coumaron, and styrene vary, and the catalyst amount temperature etc. There is also a variation in the degree of polymerization, and of course formaldehyde is also added to ensure sufficient compatibility with the epoxy resin. Therefore, when blending with the epoxy resin, it is a matter of course that ordinary coumarone resin and/or petroleum resin are blended within a range that ensures compatibility and ensures corrosion resistance and weather resistance. Furthermore, the cost of modified coumaron resins is naturally higher than that of ordinary coumaron resins due to the inclusion of formaldehyde. Therefore, it is natural that costs can be reduced by blending a mixed modified coumaron resin rather than blending only the modified coumaron resin with the epoxy resin. Petroleum resin is made by polymerizing unsaturated hydrocarbons in cracked naphtha, and although it has styrene and indene as its main components and therefore does not contain coumaron, it is different from coumaron resin both in terms of composition and physical properties. is also a similar resin. Next, the present invention will be explained in detail. In the production of the modified coumarone resin used in the present invention, raw material oils conventionally used in the production of coumarone resins are used, such as styrene, coumarone, and indensine having a boiling point range of 110 to 210°C of coke oven, gas light oil, and tar light oil. The main components are C 8 - C 11 fractions, which are derivatives thereof, and other aromatic,
Distillates containing paraffin, naphthenic, and hydrocarbon oils are used as feedstock oil. Preferably, it is a fraction obtained by processing raw oil and having a temperature of 130 to 200°C. A composition made from a modified coumaron resin containing less than 10 parts by weight of formaldehyde based on 100 parts by weight of this raw material oil for producing coumaron resin is compatible to some extent with low molecular weight epoxy resins, but is compatible with high molecular weight epoxy resins. Incompatible. Although it is possible to make compositions using modified coumaron resins containing more than 80 parts by weight of formaldehyde, the properties of conventional coumaron resins will be lost. Catalysts used in the production of the modified coumaron resin used in the present invention include inorganic acids such as sulfuric acid and phosphoric acid;
Organic acids such as para-toluenesulfonic acid or Friedel-Crafts type catalysts can be used. Any of these can be used alone or in combination of two or more. The amount used varies depending on the type of catalyst, but it is 0.1 to 40% by weight based on 100 parts by weight of feedstock oil.
That's fine. In either case, the optimum combination may be found depending on the type of catalyst, etc. The polymerization method is generally carried out by charging the raw materials into a reaction vessel equipped with a reflux condenser.
The modified coumaron resin used in the present invention can be produced by reaction at 0° C. to 150° C. for about 30 minutes to 10 hours with stirring. That is, the modified coumaron resin used in the composition of the present invention is a modified coumaron resin in which the raw material oil conventionally used for producing coumaron resin is modified with formaldehyde. In the present invention, this modified coumaron resin is blended with a conventional coumaron resin and/or petroleum resin so that the modified coumaron resin in the mixed modified coumaron resin is 50 to 90% by weight. When the modified coumaron resin accounts for less than 50% by weight of this mixed resin, the compatibility with the epoxy resin decreases. As the proportion of modified coumaron resin increases, the compatibility tends to improve, but as mentioned above, the amount of normal coumaron resin and/or petroleum resin decreases, so if it exceeds 90% by weight, corrosion resistance, weather resistance The properties of the coumaron resin deteriorate, and the cost increases as a mixed modified coumaron resin. Therefore, the preferred blending ratio is 50 to 60% by weight. This mixed modified coumaron resin has excellent compatibility with high molecular weight epoxy resins, which are considered to have poor compatibility with conventional coumaron resins. Examples of low molecular weight epoxy resins mentioned here include Epicote 827, 828, 834, 871, 872, etc. (Ciel Chemical), Araldite GY257, 252, 255, 280, etc. (Nippon Ciba Geigy), Sumiepoxy ELA-
There are general-purpose resins such as 115 and 128 (all Sumitomo Chemical).
All of these have a molecular weight of 900 or less and are also called liquid epoxy resins. Furthermore, polyolized modified resins obtained by reacting such epoxy resins with polyhydric alcohols or alkanolamines are also included in this category in the present invention. Epicoat is an example of a high molecular weight epoxy resin.
1001, 1004, 1007, 1009, etc. (Ciel Chemical),
Araldite 6071, 7071, 6084, 7097, 6097, etc. (all Nippon Ciba Geigy), Sumiepoxy ESA-
There are general-purpose resins such as 011 and 014 (both manufactured by Sumitomo Chemical), and these resins all have a molecular weight of 900 or more, and are also called solid epoxy resins. Furthermore, polyolized modified resins obtained by reacting these epoxy resins with polyhydric alcohols or alkanolamines are also included in this category in the present invention. In addition, there are epoxy resins with special skeletons such as novolak type epoxy resins and flame-retardant epoxy resins.
In the present invention, both are distinguished into low molecular weight epoxy resins and high molecular weight epoxy resins based on the molecular weight of 900 as epoxy resins. The amount of modified coumarone resin to be blended with 100 parts of these epoxy resins is 5 to 400 parts by weight, preferably 50 parts by weight.
~200 parts by weight. When it is less than 5% by weight, the effect as a modified cumaron resin composition is poor,
Although it is possible to add more than 400% by weight, this tends to impair the original properties of the epoxy resin. When the epoxy resin cured product containing the mixed modified coumaron resin composition of the present invention is made into a laminate, cast product, or paint film, it is much more transparent than those containing conventional coumaron resin or petroleum resin. We can provide you with excellent quality. The compatibility test method in the present invention is to mix the epoxy resin and the mixed resin produced in the present invention in a test tube at a ratio of 1:1 (weight ratio), heat and melt, and then
After cooling to room temperature, observe the state of turbidity. The present invention will be explained below using examples. A method for producing the modified cumaron resin used in the present invention is shown below as a reference example. Reference example Method for producing modified coumaron resin used in the present invention (1) Coal-based gas light oil and tar light oil are distilled, and the boiling point
A fraction from 135°C to 195°C was collected and used as a polymerization feedstock. 37% formalin 250 in a 14 neck flask
g, 50 g of 98% sulfuric acid, and 100 g of water were heated to 70 to 90°C, and 300 g of the above polymerization raw material was added dropwise to 90 to 100°C.
The mixture was reacted for 1 hour. After the reaction was completed, the reaction product was neutralized and washed to remove the catalyst, and unreacted fractions were removed to obtain 189 g of liquid resin. Manufacturing method of modified coumaron resin used in the present invention (2) 95% paraformaldehyde 100g, polymerization raw material oil
Mix and stir 300g. While maintaining the temperature at 30°C to 40°C, 7.0 g of BF 3 -ethyl ether complex salt was added dropwise over 12 minutes. After the addition was completed, the reaction was carried out at 90 to 100°C for 4.5 hours. After the reaction was completed, the catalyst was removed and washed to remove unreacted fractions, yielding 171 g of solid resin. The petroleum resin used in the composition of the present invention is one obtained by polymerizing unsaturated hydrocarbons present in cracked naphtha obtained by steam cracking of petroleum using a conventional catalyst, and is commercially available. It's fine and there are no restrictions. Table 1 shows examples and comparative examples in which the mixed modified coumaron resin and epoxy resin of the present invention were blended. A cured composition is prepared by adding a conventionally known epoxy resin curing agent to these formulations.
【表】
本発明の変性クマロン樹脂エポキシ樹脂組成物
は、従来のクマロン樹脂をエポキシ樹脂に配合し
たものより積層物にした場合、透明性に優れ、塗
料膜にした場合も耐食性、耐候性に優れた硬化物
を得る。
エポキシ樹脂単独の場合よりも耐水性に優れて
いる。比較的高価なエポキシ樹脂に比較的安価な
クマロン樹脂、石油樹脂の配合を可能にして、性
質を改良しながら増量材としてコスト低減に役立
つなど産業上優れた組成物である。[Table] The modified coumaron resin epoxy resin composition of the present invention has superior transparency when made into a laminate compared to conventional coumaron resin blended with epoxy resin, and has excellent corrosion resistance and weather resistance when made into a paint film. A cured product is obtained. It has better water resistance than epoxy resin alone. It is an industrially excellent composition that enables the combination of relatively inexpensive coumarone resin and petroleum resin with relatively expensive epoxy resin, and can be used as an extender to reduce costs while improving properties.
Claims (1)
のクマロン樹脂製造用原料油100重量部に対して
ホルムアルデヒド類10〜80重量部の存在下に重合
させた変性クマロン樹脂に対しクマロン樹脂及
び／又は石油樹脂を配合し、この混合変性クマロ
ン樹脂中の変性クマロン樹脂を50〜90重量％と
し、この混合変性クマロン樹脂をエポキシ樹脂
100重量部に対し、変性クマロン樹脂が５〜400重
量部となるよう配合してなる変性クマロン樹脂エ
ポキシ樹脂組成物。1 Coumaron resin and/or petroleum resin for modified coumaron resin polymerized in the presence of 10 to 80 parts by weight of formaldehyde based on 100 parts by weight of raw material oil for coumaron resin production from coal-based coke oven gas light oil or tar light oil The modified coumaron resin in this mixed modified coumaron resin is 50 to 90% by weight, and this mixed modified coumaron resin is mixed with an epoxy resin.
A modified coumaron resin epoxy resin composition, in which the modified coumaron resin is blended in an amount of 5 to 400 parts by weight per 100 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14654979A JPS5670049A (en) | 1979-11-14 | 1979-11-14 | Modified coumarone resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14654979A JPS5670049A (en) | 1979-11-14 | 1979-11-14 | Modified coumarone resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5670049A JPS5670049A (en) | 1981-06-11 |
| JPS6231020B2 true JPS6231020B2 (en) | 1987-07-06 |
Family
ID=15410165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14654979A Granted JPS5670049A (en) | 1979-11-14 | 1979-11-14 | Modified coumarone resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5670049A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0287722U (en) * | 1988-12-23 | 1990-07-11 | ||
| US10715457B2 (en) | 2010-06-15 | 2020-07-14 | Oracle International Corporation | Coordination of processes in cloud computing environments |
| US10970757B2 (en) | 2010-06-15 | 2021-04-06 | Oracle International Corporation | Organizing data in a virtual computing infrastructure |
-
1979
- 1979-11-14 JP JP14654979A patent/JPS5670049A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0287722U (en) * | 1988-12-23 | 1990-07-11 | ||
| US10715457B2 (en) | 2010-06-15 | 2020-07-14 | Oracle International Corporation | Coordination of processes in cloud computing environments |
| US10970757B2 (en) | 2010-06-15 | 2021-04-06 | Oracle International Corporation | Organizing data in a virtual computing infrastructure |
| US11657436B2 (en) | 2010-06-15 | 2023-05-23 | Oracle International Corporation | Managing storage volume in a virtual computing infrastructure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5670049A (en) | 1981-06-11 |
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