JPH0572939B2 - - Google Patents
Info
- Publication number
- JPH0572939B2 JPH0572939B2 JP8746085A JP8746085A JPH0572939B2 JP H0572939 B2 JPH0572939 B2 JP H0572939B2 JP 8746085 A JP8746085 A JP 8746085A JP 8746085 A JP8746085 A JP 8746085A JP H0572939 B2 JPH0572939 B2 JP H0572939B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- formaldehyde
- polycarbodiimide
- molecular weight
- average molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 229920003986 novolac Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 7
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 5
- -1 polymethylene Polymers 0.000 description 5
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は緻密且つ寸法変化の少ない熱硬化性樹
脂の製造方法に関するものである。
〔従来の技術〕
従来より、所謂フエノール−ホルムアルデヒド
樹脂については、酸性触媒の存在下にフエノー
ル、クレゾール等と一定量以下のホルムアルデヒ
ドとを縮合して、加熱することにより軟化溶融す
る比較的低分子量の熱可塑性樹脂状物である所謂
ノボラツク型フエノール系樹脂を得、次いでこの
樹脂をヘキサメチレンテトラミン、パラホルムア
ルデヒド等のホルムアルデヒド放出物質と加熱し
て架橋反応を起こさせ、硬化せしめるのが一つの
製造方法であつた。
〔発明が解決しようとする問題点〕
ところが、上記従来方法においては、硬化、即
ち架橋反応がベンゼン核へのホルムアルデヒド付
加に続くメチレン結合、メチレンエーテル結合の
生成を内容とするものであるから、必然的に脱水
縮合反応を伴い、又、ヘキサメチレンテトラミン
をホルムアルデヒド放出物質として使用した場合
は、ホルムアルデヒドと共にアンモニアガスの発
生することが避けられず、従つて従来方法には、
このような機構により発生するガスが硬化した樹
脂中に閉じ込められ、気泡の発生、寸法変化等の
好ましくない影響を当該樹脂に与えてしまうとい
う難点があつたのである。
〔問題点を解決するための手段〕
本発明は上述した従来技術の難点を解消して、
上記硬化機構とは原理的に全く異なる機構により
硬化時にガスが発生しないようにし、緻密且つ寸
法変化の少ない熱硬化性樹脂を製造することので
きる方法を提供することを目的としてなされたも
ので、その構成は、ノボラツク型フエノール系樹
脂と分子中に少なくとも２のカルボジイミド結合
を有するポリカルボジイミドとを包含する組成物
を適宜温度に加熱することを特徴とするものであ
る。
以下に本発明を詳細に説明する。
本発明による熱硬化性樹脂の製造方法は、ノボ
ラツク型フエノール系樹脂と、分子中に２以上の
カルボジイミド結合を有するポリカルボジイミド
とを反応させるものであつて、更に詳しくは、ノ
ボラツク型フエノール系樹脂の核置換水酸基をポ
リカルボジイミドのカルボジイミド結合に付加せ
しめて架橋反応を行うものであり、本発明に於い
てフエノール性水酸基とカルボジイミド結合とは
次式の様式で反応するものと信じられる。
[Industrial Field of Application] The present invention relates to a method for producing a thermosetting resin that is dense and exhibits little dimensional change. [Prior Art] Conventionally, so-called phenol-formaldehyde resins have been produced by condensing phenol, cresol, etc. with less than a certain amount of formaldehyde in the presence of an acidic catalyst, and producing relatively low molecular weight resins that soften and melt when heated. One manufacturing method is to obtain a so-called novolac-type phenolic resin, which is a thermoplastic resin, and then heat this resin with a formaldehyde-releasing substance such as hexamethylenetetramine or paraformaldehyde to cause a crosslinking reaction and harden it. It was hot. [Problems to be Solved by the Invention] However, in the conventional method described above, since the curing, that is, the crosslinking reaction involves the addition of formaldehyde to the benzene nucleus followed by the formation of methylene bonds and methylene ether bonds, In addition, when hexamethylenetetramine is used as a formaldehyde-releasing substance, it is inevitable that ammonia gas will be generated along with formaldehyde.
There was a problem in that the gas generated by this mechanism was trapped in the cured resin and had undesirable effects on the resin, such as the generation of bubbles and dimensional changes. [Means for Solving the Problems] The present invention solves the above-mentioned difficulties of the prior art, and
The purpose of this method is to provide a method that uses a mechanism that is fundamentally different from the above-mentioned curing mechanism to prevent gas from being generated during curing, and that can produce a thermosetting resin that is dense and has little dimensional change. Its structure is characterized by heating a composition containing a novolak type phenolic resin and a polycarbodiimide having at least two carbodiimide bonds in its molecule to an appropriate temperature. The present invention will be explained in detail below. The method for producing a thermosetting resin according to the present invention involves reacting a novolak type phenolic resin with a polycarbodiimide having two or more carbodiimide bonds in the molecule. A crosslinking reaction is carried out by adding a nuclear substituted hydroxyl group to the carbodiimide bond of polycarbodiimide, and it is believed that in the present invention, the phenolic hydroxyl group and the carbodiimide bond react in the following manner.
【化】[ka]
【式】又は[Formula] or
本発明製造方法によれば、硬化の際の架橋反応
は実質的に前記式で表された付加反応であるか
ら、硬化に際して揮発性物質が発生して得られた
樹脂に気泡が混在したり、寸法が変化したりする
ことは全くない。
又、フエノール系樹脂及びポリカルボジイミド
の双方が熱的に安定なものであり、従つて、次に
述べる実施例に明らかなように、得られる熱硬化
性樹脂の耐熱性も極めて高く、又、非常に強靱で
あり、工業的に簡単に実施し得ることと相俟つて
本発明は非常に有用なものである。
〔実施例〕
以下に本発明の実施例を示す。
実施例 １
平均分子量約500のフエノール−ホルムアルデ
ヒドによるノボラツク樹脂粉末200ｇと、平均分
子量約2000の、末端をフエニルイソシアネートで
封止したポリメチレンポリフエニルポリカルボジ
イミド40ｇをボールミル中で４時間混合した。混
合物を180℃に加熱した金型に入れ、圧力５Kg／
cm2で10分間加熱すると、黄色の硬化樹脂が得られ
た。
この樹脂の特性は次の通りであつた。
密度 1.28ｇ／cm3
曲げ強度 205Kg／cm2
400℃までの重量減少率 10％
限界酸素指数 52
実施例 ２
平均分子量約500のフエノール−ホルムアルデ
ヒドによるノボラツク樹脂粉末100ｇと、平均分
子量約2000の、末端をフエニルイソシアネートで
封止したポリメチレンポリフエニルポリカルボジ
イミド100ｇをボールミル中で４時間混合した。
混合物を180℃に加熱した金型に入れ、圧力５
Kg／cm2で10分間加熱すると、黄色の硬化樹脂が得
られた。
この樹脂の特性は次の通りであつた。
密度 1.32ｇ／cm3
曲げ強度 219Kg／cm2
400℃までの重量減少率 ５％
限界酸素指数 56
実施例 ３
平均分子量約500のフエノール−ホルムアルデ
ヒドによるノボラツク樹脂粉末40ｇと、平均分子
量約2000の、末端をフエニルイソシアネートで封
止したポリメチレンポリフエニルポリカルボジイ
ミド200ｇをボールミル中で４時間混合した。混
合物を180℃に加熱した金型に入れ、圧力５Kg／
cm2で10分間加熱すると、黄色の硬化樹脂が得られ
た。
この樹脂の特性は次の通りであつた。
密度 1.29ｇ／cm3
曲げ強度 214Kg／cm2
400℃までの重量減少率 ３％
限界酸素指数 56
実施例 ４
平均分子量約800のフエノール−ホルムアルデ
ヒドによるノボラツク樹脂粉末100ｇと、平均分
子量約2000の、末端をフエニルイソシアネートで
封止したポリメチレンポリフエニルポリカルボジ
イミド100ｇをＮ−メチルピロリドン1000mlに溶
解した。
この溶液をガラスプレート上に塗布し、溶媒を
留去して皮膜を作つた後、更に300℃で５時間熱
処理したものの性能は次の通りであつた。
体積固有抵抗率 1016（Ω・cm）
絶縁破壊強さ 15（KV／mm）
実施例 ５
平均分子量約800のフエノール−ホルムアルデ
ヒドによるノボラツク樹脂粉末10ｇと、平均分子
量約3000の、末端をフエニルイソシアネートで封
止したポリメチレンポリフエニルポリカルボジイ
ミド10ｇをボールミル中で混合した。
この混合物とガラスクロスから作つた200℃の
成型品の物性は次の通りであつた。
ガラス含有率 40％
密度 1.53ｇ／cm3
曲げ強度 8300Kg／cm2
曲げ弾性率 152000Kg／cm2
According to the production method of the present invention, since the crosslinking reaction during curing is essentially an addition reaction expressed by the above formula, volatile substances may be generated during curing and bubbles may be mixed in the resulting resin. The dimensions do not change at all. Furthermore, both the phenolic resin and the polycarbodiimide are thermally stable, and therefore, as is clear from the examples described below, the resulting thermosetting resin has extremely high heat resistance. The present invention is very useful because it is extremely strong and can be easily implemented industrially. [Example] Examples of the present invention are shown below. Example 1 200 g of a phenol-formaldehyde novolak resin powder having an average molecular weight of about 500 and 40 g of phenyl isocyanate-terminated polymethylene polyphenyl polycarbodiimide having an average molecular weight of about 2000 were mixed in a ball mill for 4 hours. The mixture was put into a mold heated to 180℃, and the pressure was 5Kg/
After heating at cm2 for 10 minutes, a yellow cured resin was obtained. The properties of this resin were as follows. Density 1.28 g/cm 3 Bending strength 205 Kg/cm 2 Weight loss rate up to 400°C 10% Limiting oxygen index 52 Example 2 100 g of novolac resin powder made from phenol-formaldehyde with an average molecular weight of about 500 and a terminal powder with an average molecular weight of about 2000 100 g of polymethylene polyphenyl polycarbodiimide sealed with phenyl isocyanate was mixed in a ball mill for 4 hours.
Place the mixture in a mold heated to 180℃ and apply pressure 5
After heating at Kg/cm 2 for 10 minutes, a yellow cured resin was obtained. The properties of this resin were as follows. Density 1.32 g/cm 3 Bending strength 219 Kg/cm 2 Weight loss rate up to 400°C 5% Limiting oxygen index 56 Example 3 40 g of novolac resin powder made from phenol-formaldehyde with an average molecular weight of about 500 and the terminal 200 g of polymethylene polyphenyl polycarbodiimide sealed with phenyl isocyanate was mixed in a ball mill for 4 hours. The mixture was put into a mold heated to 180℃, and the pressure was 5Kg/
After heating at cm2 for 10 minutes, a yellow cured resin was obtained. The properties of this resin were as follows. Density 1.29 g/cm 3 Bending strength 214 Kg/cm 2 Weight loss rate up to 400°C 3% Limiting oxygen index 56 Example 4 100 g of novolak resin powder made from phenol-formaldehyde with an average molecular weight of about 800, and a terminal powder with an average molecular weight of about 2000 100 g of polymethylene polyphenyl polycarbodiimide sealed with phenyl isocyanate was dissolved in 1000 ml of N-methylpyrrolidone. This solution was applied onto a glass plate, the solvent was distilled off to form a film, and the film was further heat-treated at 300°C for 5 hours, and its performance was as follows. Specific volume resistivity 10 16 (Ω・cm) Dielectric breakdown strength 15 (KV/mm) Example 5 10 g of novolak resin powder made of phenol-formaldehyde with an average molecular weight of about 800 and phenyl isocyanate terminals with an average molecular weight of about 3000. 10 g of encapsulated polymethylene polyphenyl polycarbodiimide were mixed in a ball mill. The physical properties of a molded product made from this mixture and glass cloth at 200°C were as follows. Glass content 40% Density 1.53g/cm 3 Bending strength 8300Kg/cm 2 Flexural modulus 152000Kg/cm 2
Claims (1)
なくとも２のカルボジイミド結合を有するポリカ
ルボジイミドとを包含する組成物を適宜温度に加
熱することを特徴とする熱硬化性樹脂の製造方
法。1. A method for producing a thermosetting resin, which comprises heating a composition containing a novolak type phenolic resin and a polycarbodiimide having at least two carbodiimide bonds in the molecule to an appropriate temperature.
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60087460A JPS61246245A (en) | 1985-04-25 | 1985-04-25 | Production of thermosetting resin |
| DE3643238A DE3643238C2 (en) | 1985-03-29 | 1986-03-21 | |
| DE19863643239 DE3643239C2 (en) | 1985-03-29 | 1986-03-21 | |
| DE19863609687 DE3609687A1 (en) | 1985-03-29 | 1986-03-21 | DUROPLASTIC RESIN AND METHOD FOR THE PRODUCTION THEREOF |
| DE3643241A DE3643241C2 (en) | 1985-03-29 | 1986-03-21 | |
| KR1019860002223A KR900008986B1 (en) | 1985-03-29 | 1986-03-25 | Process for the preparation of thermosetting resin |
| FR868604382A FR2579600B1 (en) | 1985-03-29 | 1986-03-26 | THERMOSETTING RESIN BASED ON CROSSLINKED POLYCARBODIIMIDES AND PREPARATION THEREOF |
| CA000505286A CA1269481A (en) | 1985-03-29 | 1986-03-27 | Thermosetting resin and a method for producing it |
| GB8607840A GB2177710B (en) | 1985-03-29 | 1986-03-27 | A thermosetting resin and a method for producing it |
| GB8807544A GB2201422B (en) | 1985-03-29 | 1988-03-30 | A thermosetting resin and a method for producing it |
| GB8807543A GB2201421B (en) | 1985-03-29 | 1988-03-30 | A thermosetting resin and a method for producing it |
| US07/225,598 US5079326A (en) | 1985-03-29 | 1988-07-26 | Thermosetting resin and a method for producing it |
| KR1019900010975A KR910003767B1 (en) | 1985-03-29 | 1990-07-19 | Method for producing thermosetting resin |
| KR1019900010974A KR910003766B1 (en) | 1985-03-29 | 1990-07-19 | A method for producing thermosetting resin |
| US07/753,393 US5321101A (en) | 1985-03-29 | 1991-08-30 | Thermosetting resin and a method for producing it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60087460A JPS61246245A (en) | 1985-04-25 | 1985-04-25 | Production of thermosetting resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61246245A JPS61246245A (en) | 1986-11-01 |
| JPH0572939B2 true JPH0572939B2 (en) | 1993-10-13 |
Family
ID=13915486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60087460A Granted JPS61246245A (en) | 1985-03-29 | 1985-04-25 | Production of thermosetting resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61246245A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020012A1 (en) * | 1994-01-25 | 1995-07-27 | Nisshinbo Industries, Inc. | Sheet material and process for producing the same |
| EP0789060B1 (en) * | 1995-04-05 | 2002-07-31 | Nisshinbo Industries, Inc. | Gasket for compressor of refrigerator or the like |
| JP2004269691A (en) | 2003-03-07 | 2004-09-30 | Nitto Denko Corp | Polycarbodiimide copolymer and method for producing the same |
| JP2004292602A (en) | 2003-03-26 | 2004-10-21 | Nitto Denko Corp | Underfill adhesive film and semiconductor device using the same |
-
1985
- 1985-04-25 JP JP60087460A patent/JPS61246245A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61246245A (en) | 1986-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DD240210A5 (en) | CHEMICALLY HARDENED RESINS FROM COMPOUNDS CONTAINING 1-OXA-1-AZA-TETRALINGRUPPEN AND CYCLOALIPHATIC EPOXY RESINS, METHOD FOR THE PRODUCTION AND PREPARATION THEREOF | |
| CN116218037A (en) | Epoxy plastic package material of modified silicon dioxide grafted epoxy resin and preparation method thereof | |
| JPH0572939B2 (en) | ||
| JPH06100665A (en) | Epoxy resin composition | |
| JPS6053516A (en) | High-purity phenolic resin and its preparation | |
| JPS63105473A (en) | Manufacture of carbon plate for fuel cell | |
| CN117510759A (en) | Thermosetting phenolic resin for 3D printing and preparation method thereof | |
| US2875179A (en) | Conversion of thermoplastic resins to thermoset resins | |
| JPH0681775B2 (en) | Method for producing polyhydroxy compound | |
| JPS6248974B2 (en) | ||
| JPH0569127B2 (en) | ||
| JPH09124759A (en) | Phenol novolak resin composition | |
| CN111303361A (en) | Special phenolic resin for environment-friendly high-strength precoated sand | |
| GB2095680A (en) | Reactive accelerators for acid- anhydride-hardened resin systems | |
| JPS6115085B2 (en) | ||
| CN110698648A (en) | Preparation method of novel epoxy resin composition | |
| JPS5823413B2 (en) | phenol resin products | |
| JP2010159348A (en) | Phenol resin-cured article | |
| JPS6351419A (en) | Production of thermosetting hydrocarbon resin | |
| KR20250099439A (en) | Curable composition | |
| CN116425932A (en) | A kind of preparation method of norbornene modified phenolic resin | |
| SU823389A1 (en) | Method of binder production | |
| CN121108684A (en) | A boron nitride-epoxy glass polymer thermally conductive composite material and its preparation method | |
| JPH01123856A (en) | Thermosetting resin molding material | |
| JPS6328925B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |