JPS6233247B2 - - Google Patents
Info
- Publication number
- JPS6233247B2 JPS6233247B2 JP56084731A JP8473181A JPS6233247B2 JP S6233247 B2 JPS6233247 B2 JP S6233247B2 JP 56084731 A JP56084731 A JP 56084731A JP 8473181 A JP8473181 A JP 8473181A JP S6233247 B2 JPS6233247 B2 JP S6233247B2
- Authority
- JP
- Japan
- Prior art keywords
- thpa
- anhydride
- epoxy resin
- isomer mixture
- present
- 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
- 239000000203 mixture Substances 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 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 5
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 amine compounds Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は液状の酸無水物系硬化剤を含有する硬
化性エポキシ樹脂組成物に関するものである。
エポキシ樹脂硬化剤としては種々のアミン系化
合物及び酸無水物系化合物が主として使用されて
いる。酸無水物系硬化剤は配合物のポツトライフ
が長い、硬化時の発熱が少ない等の特徴があり、
多くの電気絶縁材料分野に使用されている。これ
らには無水マレイン酸、無水フタル酸、テトラヒ
ドロ無水フタル酸、ヘキサヒドロ無水フタル酸、
メチルテトラヒドロ無水フタル酸、メチルヘキサ
ヒドロ無水フタル酸などが知られているが、一般
に無水マレイン酸（mp.202℃）、無水フタル酸
（mp.130℃）、テトラヒドロ無水フタル酸
（mp.104℃）の如く高融点の酸無水物はエポキシ
樹脂の硬化剤とした場合は、均一に混合するため
に融点以上に加熱しなければならず、その結果エ
ポキシ樹脂組成物のポツトライフが短くなるなど
の欠点がある。このため一般にエポキシ樹脂硬化
剤として酸無水物を使用する場合は、常温で液状
であることが好ましい。
本発明者は、この問題点を考慮し、鋭意検討し
た結果、室温以下で液状安定性のある酸無水物に
ついて本発明を完成したものである。
即ち本発明は、△4-テトラヒドロ無水フタル酸
（以下△４−THPA）の異性体混合物（）とメ
チル―△４―テトラヒドロ無水フタル酸（以下
Me―△４―THPA）の異性体混合物（）と
を、（）と（）の混合比が95：５〜５：95で
ある常温又はさらに低温で液状の酸無水物を調製
し、これをエポキシ樹脂に配合した硬化性エポキ
シ樹脂組成物に関するものである。
本発明の異性体混合物とはシクロヘキセン環の
２重結合を転移して得られる△１，△２，△３及
び△４の異性体２〜４種の混合物である。又Me
―△４―THPAは３―メチル（以下３―Me―△
４―THPA）と４―メチル（以下４―Me―△４
―THPA）がありそのいずれでも良い。
異性体混合物の調製は△４―THPAとMe―△
４―THPAをそれぞれ別々に異性化して後、混合
してもよく、あるいは△４―THPAとMe―△４
―THPAを先に混合してから異性化しても何ら差
支えない。異性化のために使用される触媒として
は例えば五酸化リン、硫酸、ポリリン酸、メタリ
ン酸、酸性硫酸ナトリウム、三フツ化ホウ素コン
プレツクス、金属パラジユウム、金属ルテニウム
等が挙げられ、これらの触媒を△４―THPA，
Me―△４―THPAそれぞれ単独又はその混合物
100重量部当り0.1〜３重量部加え、反応温度120
〜240℃、反応時間0.5〜10時間の条件で処理すれ
ばよい。
本法により得られた異性体混合物は必要に応じ
て触媒を過により除去することも可能である
し、さらには蒸留により精製してもよい。
本発明にもとづく酸無水物とエポキシ樹脂との
混合物は常温で液状になるため均一な組成物を得
やすく、混合時に加熱が必要でないのでポツトラ
イフを短くするという欠点がない。得られた硬化
樹脂は優れた電気特性、機械特性、化学特性など
を示す。本発明に適用されるエポキシ樹脂は、分
子中にエポキシ基を平均１個以上持つもので例え
ば多価フエノール、多価アルコールのポリグリシ
ジルエーテル類、多塩基酸のポリグリシジルエス
テル類、窒素塩基のＮ―グリシジル誘導体、脂環
式エポキシ樹脂など一般に知られているエポキシ
樹脂がある。
本発明の組成物には公知の硬化促進剤、充填
剤、希釈剤、難燃剤、その他の変成剤等を含むこ
とができる。
製造例 １〜５
第１表の如く、原料THPA混合物に五酸化リン
１ｇを加え、窒素気流下に200℃、３時間反応
し、生成物を減圧蒸留して淡黄色の液状異性体混
合物をそれぞれ得た。生成物の特性も合せて第１
表に示す。更に、各製造例における生成物中の
THPA異性体混合物の異性体組成（％）（GLCに
よる）を第２表に示す。
The present invention relates to a curable epoxy resin composition containing a liquid acid anhydride curing agent. Various amine compounds and acid anhydride compounds are mainly used as epoxy resin curing agents. Acid anhydride curing agents have characteristics such as long pot life of the compound and low heat generation during curing.
Used in many electrical insulation materials fields. These include maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. are known, but generally maleic anhydride (mp.202℃), phthalic anhydride (mp.130℃), tetrahydrophthalic anhydride (mp.104℃) ) When acid anhydrides with high melting points are used as curing agents for epoxy resins, they must be heated above the melting point in order to mix uniformly, resulting in disadvantages such as a shortened pot life of the epoxy resin composition. There is. For this reason, when an acid anhydride is generally used as an epoxy resin curing agent, it is preferably liquid at room temperature. The present inventor took this problem into consideration and, as a result of intensive studies, completed the present invention regarding an acid anhydride that is stable in liquid form below room temperature. That is, the present invention provides an isomer mixture of Δ4- tetrahydrophthalic anhydride (hereinafter referred to as Δ4- THPA) and methyl- Δ4 -tetrahydrophthalic anhydride (hereinafter referred to as Δ4-THPA).
A liquid acid anhydride is prepared from the isomer mixture (Me-△ 4 -THPA) at room temperature or at a lower temperature with a mixing ratio of () and () of 95:5 to 5:95, and this is The present invention relates to a curable epoxy resin composition blended with an epoxy resin. The isomer mixture of the present invention is a mixture of two to four isomers of Δ 1 , Δ 2 , Δ 3 and Δ 4 obtained by rearranging the double bond of the cyclohexene ring. MataMe
-△ 4 -THPA is 3-methyl (hereinafter 3-Me-△
4 -THPA) and 4-methyl (hereinafter referred to as 4-Me-△ 4
-THPA), either of which is fine. Preparation of isomer mixture is △ 4 -THPA and Me- △
4 - THPA may be isomerized separately and then mixed, or △ 4 - THPA and Me - △ 4
-There is no problem in mixing THPA first and then isomerizing it. Examples of catalysts used for isomerization include phosphorus pentoxide, sulfuric acid, polyphosphoric acid, metaphosphoric acid, acidic sodium sulfate, boron trifluoride complex, metal palladium, metal ruthenium, etc. 4 -THPA,
Me-△ 4 -THPA each alone or a mixture thereof
Add 0.1 to 3 parts by weight per 100 parts by weight, reaction temperature 120
The treatment may be carried out under conditions of ~240°C and reaction time of 0.5 to 10 hours. The isomer mixture obtained by this method may be purified by distillation or the catalyst may be removed by filtration, if necessary. Since the mixture of acid anhydride and epoxy resin according to the present invention becomes liquid at room temperature, it is easy to obtain a uniform composition, and since heating is not required during mixing, there is no disadvantage of shortening the pot life. The resulting cured resin exhibits excellent electrical, mechanical, and chemical properties. The epoxy resins applied to the present invention have an average of one or more epoxy groups in the molecule, such as polyhydric phenols, polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polybasic acids, N of nitrogen bases, etc. - There are commonly known epoxy resins such as glycidyl derivatives and alicyclic epoxy resins. The composition of the present invention may contain known curing accelerators, fillers, diluents, flame retardants, other modifying agents, and the like. Production Examples 1 to 5 As shown in Table 1, 1 g of phosphorus pentoxide was added to the raw material THPA mixture, reacted at 200°C for 3 hours under a nitrogen stream, and the product was distilled under reduced pressure to obtain pale yellow liquid isomer mixtures. Obtained. In addition to the characteristics of the product, the first
Shown in the table. Furthermore, in the product in each production example,
The isomer composition (%) of the THPA isomer mixture (according to GLC) is shown in Table 2.
【表】【table】
【表】
実施例 １〜５
製造例１〜５で得られた酸無水物の異性体混合
物をエポキシ樹脂に配合し、対応する実施例１〜
５の特性を第３表に示した。[Table] Examples 1 to 5 The isomer mixtures of acid anhydrides obtained in Production Examples 1 to 5 were blended with epoxy resin, and the corresponding Examples 1 to 5 were mixed with epoxy resins.
The characteristics of No. 5 are shown in Table 3.
【表】【table】
Claims (1)
有するエポキシ化合物に、テトラヒドロ無水フタ
ル酸異性体混合物（）と、メチル―テトラヒド
ロ無水フタル酸異性体混合物（）を配合し、前
記（）と（）との混合比が95：５及至５：95
であることを特徴とする硬化性エポキシ樹脂組成
物。1. A tetrahydrophthalic anhydride isomer mixture () and a methyl-tetrahydrophthalic anhydride isomer mixture () are blended into an epoxy compound having an average of one or more adjacent epoxy groups per molecule, and the above () and () are mixed. Mixing ratio between 95:5 and 5:95
A curable epoxy resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8473181A JPS57198725A (en) | 1981-06-01 | 1981-06-01 | Curable epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8473181A JPS57198725A (en) | 1981-06-01 | 1981-06-01 | Curable epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57198725A JPS57198725A (en) | 1982-12-06 |
| JPS6233247B2 true JPS6233247B2 (en) | 1987-07-20 |
Family
ID=13838832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8473181A Granted JPS57198725A (en) | 1981-06-01 | 1981-06-01 | Curable epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57198725A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647701A (en) * | 1970-01-06 | 1972-03-07 | Vanderbilt Co R T | Process for preparing a mixture of 4-methyl-delta-tetrahydrophthalic anhydrides as a curing agent |
| JPS511447A (en) * | 1974-06-24 | 1976-01-08 | Asahi Denka Kogyo Kk | |
| JPS5297945A (en) * | 1976-02-12 | 1977-08-17 | Hitachi Chem Co Ltd | Acid anhydride composition |
| JPS55115879A (en) * | 1979-02-28 | 1980-09-06 | Mitsubishi Petrochem Co Ltd | Isomerization of tetrahydrophthalic anhydride and its derivative |
-
1981
- 1981-06-01 JP JP8473181A patent/JPS57198725A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647701A (en) * | 1970-01-06 | 1972-03-07 | Vanderbilt Co R T | Process for preparing a mixture of 4-methyl-delta-tetrahydrophthalic anhydrides as a curing agent |
| JPS511447A (en) * | 1974-06-24 | 1976-01-08 | Asahi Denka Kogyo Kk | |
| JPS5297945A (en) * | 1976-02-12 | 1977-08-17 | Hitachi Chem Co Ltd | Acid anhydride composition |
| JPS55115879A (en) * | 1979-02-28 | 1980-09-06 | Mitsubishi Petrochem Co Ltd | Isomerization of tetrahydrophthalic anhydride and its derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57198725A (en) | 1982-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0009645B1 (en) | 5-(2,5-diketotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, its use as curing agent for epoxy resins and as raw material for the production of polyimides, epoxy resins containing it, and their use in the preparation of various articles, and powder coating compositions | |
| EP0018949B1 (en) | Curable epoxy resin mixtures and curing accelerators therefore | |
| US2890204A (en) | Epoxy resin compositions | |
| US4371688A (en) | Substituted cyclohexane-1,2-dicarboxylic anhydrides and epoxy resins containing same | |
| JPS6233247B2 (en) | ||
| US3764584A (en) | Curable compositions | |
| JP3142651B2 (en) | Process for producing saturated alicyclic dicarboxylic anhydride | |
| US3620983A (en) | {11 -methylglycidyl-isocyanurates | |
| JPH0363967B2 (en) | ||
| US3560411A (en) | Epoxyalkyl esters of endo-methylene hexahydrophthalic acid | |
| JP2533592B2 (en) | Epoxy resin composition | |
| US3470132A (en) | Thermocurable composition of epoxy resins and mixed polycarboxylic acid anhydrides | |
| US2992196A (en) | Polyepoxide-dicarboxylic anhydride compositions | |
| JPS6053523A (en) | Manufacture of epoxide resin molding material | |
| US3404195A (en) | Process for improving the thermal properties of hardened epoxide resins | |
| JP4774591B2 (en) | Method for producing low-viscosity liquid acid anhydride and epoxy resin composition | |
| JPS6157327B2 (en) | ||
| JPS5825325A (en) | Curing agent for epoxy resin | |
| US3745179A (en) | Diene synthesis using isoprene and citraconic acid anhydride,and hydrogenation of synthesis product | |
| JP2533593B2 (en) | Epoxy resin composition | |
| JPS6136526B2 (en) | ||
| JPS6133854B2 (en) | ||
| JP2002155069A (en) | Method for producing low-viscosity liquid acid anhydride and epoxy resin composition | |
| US4507460A (en) | Epoxy resin composition | |
| JPH01123818A (en) | Epoxy resin composition |