JPS624720A - Novel resorcinol resin and its production - Google Patents
Novel resorcinol resin and its productionInfo
- Publication number
- JPS624720A JPS624720A JP14414785A JP14414785A JPS624720A JP S624720 A JPS624720 A JP S624720A JP 14414785 A JP14414785 A JP 14414785A JP 14414785 A JP14414785 A JP 14414785A JP S624720 A JPS624720 A JP S624720A
- Authority
- JP
- Japan
- Prior art keywords
- dicyclopentadiene
- resorcinol
- resorcinol resin
- catalyst
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は下記一般式〔１〕
〔式中、口は平均値Ｏ〜１５を示す。〕で表わさ枕る新
規レゾルシノール樹脂及びその製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is based on the following general formula [1] [wherein the value indicates an average value of 0 to 15]. This invention relates to a new resorcinol resin represented by the following formula and a method for producing the same.
〔従来の技術及び発明が解決しようとする問題点〕フェ
ノール樹脂及びレゾルシノール樹脂あるいは、レゾルシ
ノール変性フェノール樹脂は、機械的特性、電気的特性
、耐熱性、加工特性に優れているため電気・電子材料及
び塗料関係に広く使用されている。[Prior art and problems to be solved by the invention] Phenol resins and resorcinol resins or resorcinol-modified phenol resins have excellent mechanical properties, electrical properties, heat resistance, and processing properties, so they are used in electrical and electronic materials and Widely used in paints.
最近、電子部品、中でも封止材料樹脂及び硬化剤に４３
いでは、集積回路の高集積化に伴い、耐熱性の向上、硬
化後の残留応力の緩和が要求される一方、プリント配線
１．を盤用樹脂及び硬化剤では、耐熱性、可撓性の向上
が要求されている。Recently, 43% has been applied to electronic parts, especially sealing material resins and hardening agents.
With the increase in the degree of integration of integrated circuits, improvements in heat resistance and relaxation of residual stress after curing are required. Resins and curing agents for discs are required to have improved heat resistance and flexibility.
従来、封止用樹脂材料において、硬化剤として用いられ
ているフェノールノボラックが硬化体に対して残留応力
緩和能、可撓性付与能が無いのに対し、それらをもつ硬
化剤を鋭意検討した。その結果、本発明の新規レゾルシ
ノール樹脂とぞの製造方法を見出した。Phenol novolak, which has conventionally been used as a curing agent in resin materials for sealing, does not have the ability to relieve residual stress or impart flexibility to the cured product, so we have intensively investigated curing agents that have these properties. As a result, a method for producing the novel resorcinol resin of the present invention was discovered.
で表わされる新規レゾルシノール樹脂及びレゾルシノー
ル類とジシクロペンタジェンを触媒の存在下で重合させ
ることを特徴とする上記レゾルシノール樹脂の装造法に
関するものである。The present invention relates to a novel resorcinol resin represented by the following formula and a method for preparing the resorcinol resin, which is characterized by polymerizing resorcinols and dicyclopentadiene in the presence of a catalyst.
従来のフェノールノボラック樹脂を硬化剤とした場合に
比べ、フェノールのかわりにレゾルシノールを用いるこ
とにより、水Ｉ１Ｍ当吊を上げ、硬化体の架橋密度を上
げることにより、耐熱性の向上をはかり、メチレンジヨ
イントのかわりに、ジシクロペンタジェンを用いること
により可撓性、応力緩和性をもたけることができる。Compared to conventional phenol novolak resins used as curing agents, by using resorcinol instead of phenol, the water I1M capacity is increased and the crosslinking density of the cured product is increased, thereby improving heat resistance. By using dicyclopentadiene instead of Into, flexibility and stress relaxation properties can be imparted.
以下本発明を詳述する。The present invention will be explained in detail below.
本発明の新規レゾルシノール樹脂は、レゾルシノール類
とジシクロペンタジェンを触媒を用いて重合させること
により得られる。ここで使用されるレゾルシノール類と
は、レゾルシノール、２−メチルレゾルシノール等であ
るが、これにフェノール、クレゾール等のフェノール類
を混合し、共重合することも可能である。The novel resorcinol resin of the present invention is obtained by polymerizing resorcinols and dicyclopentadiene using a catalyst. The resorcinols used here include resorcinol, 2-methylresorcinol, etc., but it is also possible to mix phenols such as phenol and cresol with these and copolymerize them.
触媒としては、ルイス酸であれば使用でき、ＡＪ２Ｃ，
ｅ３、ＢＦ５ 、Ｚｎ ＣＪ２ｚ 、ｏ−トルエンスル
ホン酸、ｒ； ｃ、ｅ◆、Ｈ２ＳＯ４等を挙げることが
できる。As a catalyst, any Lewis acid can be used, such as AJ2C,
Examples include e3, BF5, ZnCJ2z, o-toluenesulfonic acid, r;c, e♦, H2SO4, and the like.
触媒は単一あるいは、混合して使用することができる。A single catalyst or a mixture of catalysts can be used.
触媒の添加量は、ジシクロペンタジェン１モルに対しＵ
、 ０．００１〜０．１モル好ましくは、ｏ、ｏｏｓ
〜０．０５モルである。レゾルシノール類は、ジシクロ
ペンタジェン１モルに対し、０．５モル〜２０モル、好
ましくは０．８〜８．０モルである。各物質の重合方法
としては、ジシクロペンタジェンとレゾルシノール類の
混合物に触媒を加えてもよいし、レゾルシノール類と触
媒の混合物にジシクロペンタジェンを加えてもよい。添
加時間は、配合によって異なるが、０．１へ・１０時間
である。添加後反応系をさらに数時間反応させる。レゾ
ルシノール類とジシクロペンタジェンの重合反応温度は
、２０〜１８０℃で好ましくは６０〜１２０℃である。The amount of catalyst added is U per mole of dicyclopentadiene.
, 0.001 to 0.1 mol, preferably o, oos
~0.05 mol. The amount of resorcinols is 0.5 to 20 mol, preferably 0.8 to 8.0 mol, per 1 mol of dicyclopentadiene. As a method for polymerizing each substance, a catalyst may be added to a mixture of dicyclopentadiene and resorcinols, or dicyclopentadiene may be added to a mixture of resorcinols and a catalyst. The addition time varies depending on the formulation, but is 0.1 to 10 hours. After the addition, the reaction system is allowed to react for several more hours. The polymerization reaction temperature of resorcinols and dicyclopentadiene is 20 to 180°C, preferably 60 to 120°C.
重合反応によって得られた樹脂は、用途によって、未反
応モノマーを除去する必要があり、また残存する触媒も
系外に取り出す必要がある。Depending on the use of the resin obtained by the polymerization reaction, it is necessary to remove unreacted monomers, and it is also necessary to remove the remaining catalyst from the system.
未反応モノマーの除去法としては、減圧蒸留又は分別沈
澱が行えるが、またそれらを組み合わせた方法でもよい
。触媒の除去に関しては、ＢＦ３等では減圧蒸留により
モノマーと同口１に除去が可能であるが、ＡＪＩＣＪＩ
！３その他の触媒除去においては、溶剤分離法によって
取り除くこともできる。As a method for removing unreacted monomers, vacuum distillation or fractional precipitation can be used, but a combination of these methods may also be used. Regarding the removal of the catalyst, with BF3 etc., it is possible to remove it in the same volume as the monomer by vacuum distillation, but with AJICJI
! 3. Other catalysts can also be removed by a solvent separation method.
以Ｆ、減圧蒸留、分別沈澱、水洗等により不純物を取り
除いた後、減圧濃縮し一般式（Ｉ）で示される新規レゾ
ルシノール樹脂を得る。Thereafter, impurities are removed by distillation under reduced pressure, fractional precipitation, washing with water, etc., and then concentrated under reduced pressure to obtain a new resorcinol resin represented by general formula (I).
以下に実施例を挙げて説明するが、これらの実施例によ
って本発明は制限されるものではない。以下に部とある
のは、いずれも重量部である。Examples will be described below, but the present invention is not limited to these Examples. All parts below are parts by weight.
実施例ル
ゾルシノール ３３３部
ジシクロペンタジェン １３８部
を、温度計、冷却器、撹拌装置、及び滴下管をイ１けた
反応器内に仕込み、８０±５℃に保ち撹拌しながら、エ
チルエーテル５０部に三フッ化ホウ素エーテル錯体（三
フッ化ホウ素４７％）５部を溶解した液を２時間かけて
滴下した。Example 333 parts of lusorcinol and 138 parts of dicyclopentadiene were placed in a reactor equipped with a thermometer, a condenser, a stirrer, and a dropping tube, and the mixture was added to 50 parts of ethyl ether while stirring while maintaining the temperature at 80±5°C. A solution containing 5 parts of boron trifluoride ether complex (47% boron trifluoride) was added dropwise over 2 hours.
反応液をさらに８０±５°Ｃに２（時間保持、撹拌 ４
した後、メタノール５００部に溶解した。The reaction solution was further heated to 80±5°C for 2 hours (maintained and stirred for 4 hours).
After that, it was dissolved in 500 parts of methanol.
メタノール溶液に水２５０部を加え、不溶解弁を回収し
、その中に残る溶媒を加熱留去し、目的とする重合物を
３３０部得た。250 parts of water was added to the methanol solution, the insoluble valve was recovered, and the solvent remaining therein was distilled off under heating to obtain 330 parts of the desired polymer.
この重合物の特性を次の表−１及び添付の第１図ないし
第３図に示した。The properties of this polymer are shown in the following Table 1 and the attached Figures 1 to 3.
表−１
１）ＧＰＣ法による、ポリスチレン換綽値２）エタノー
ル溶液
カラム：ＴＳＫ ＧＥＬ ４０００ＨＸＬｘ１＋３
０００ＨＸＬｘ１＋２０００ｔｌＸＬｘ２溶媒：ＴＩ−
ＩＦ、 １ｍ、ｅ／ｍｉｎ 。Table 1 1) Polystyrene conversion value by GPC method 2) Ethanol solution column: TSK GEL 4000HXLx1+3
000HXLx1+2000tlXLx2 Solvent: TI-
IF, 1m, e/min.
検出：Ｒ■ ３）日本電子製 Ｆｘ−９００，溶媒量メタノールDetection: R■ 3) JEOL Fx-900, solvent amount methanol
第１図は本発明の実施例１化合物のＧＰＣ（ゲル・バー
ミコシ」ン・クロマトグラフ）を示す図表、第２図は同
一ヒのＩＲを示す図表、第３図は同一ヒのＮ Ｍ Ｒを
承り図表である。
（別 紙）
２、特許請求の範囲
１）下記一般式（Ｉ）
〔式中、ｎは平均値Ｏ〜１５を示す。〕で表わされる新
規レゾルシノール樹脂。
２）レゾルシノール類とジシクロペンタジェンを触媒の
存在下で重合させることを特徴とする下記一般式（Ｉ）
で示される新規レゾルシノール樹脂の製造法。
（Ｉ）Fig. 1 is a chart showing the GPC (gel vermicosin chromatography) of the compound of Example 1 of the present invention, Fig. 2 is a chart showing the IR of the same human, and Fig. 3 is a chart showing the NMR of the same human. This is an acceptance chart. (Attachment) 2. Claims 1) The following general formula (I) [wherein n represents an average value of 0 to 15]. ] A new resorcinol resin. 2) The following general formula (I), characterized in that resorcinols and dicyclopentadiene are polymerized in the presence of a catalyst.
A method for producing a new resorcinol resin shown in (I)
Claims (1)
存在下で重合させることを特徴とする下記一般式〔 I
〕で示される新規レゾルシノール樹脂の製造法。 ▲数式、化学式、表等があります▼ 〔 I 〕 〔式中、ｎは平均値０〜１５を示す。〕[Claims] 1) The following general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, n indicates an average value of 0 to 15. ] A new resorcinol resin represented by 2) The following general formula [I] characterized by polymerizing resorcinols and dicyclopentadiene in the presence of a catalyst
] A method for producing a new resorcinol resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, n indicates an average value of 0 to 15. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14414785A JPH0674321B2 (en) | 1985-07-01 | 1985-07-01 | Novel resorcinol resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14414785A JPH0674321B2 (en) | 1985-07-01 | 1985-07-01 | Novel resorcinol resin and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS624720A true JPS624720A (en) | 1987-01-10 |
| JPH0674321B2 JPH0674321B2 (en) | 1994-09-21 |
Family
ID=15355307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14414785A Expired - Lifetime JPH0674321B2 (en) | 1985-07-01 | 1985-07-01 | Novel resorcinol resin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674321B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0798324A1 (en) * | 1996-03-29 | 1997-10-01 | Ceca S.A. | Phenol-diene novolac resins, process for their preparation and rubber compositions containing said resins |
| US7135539B2 (en) | 2000-09-08 | 2006-11-14 | Schenectady International Inc. | Novolac resins, process for preparing them and uses thereof |
-
1985
- 1985-07-01 JP JP14414785A patent/JPH0674321B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0798324A1 (en) * | 1996-03-29 | 1997-10-01 | Ceca S.A. | Phenol-diene novolac resins, process for their preparation and rubber compositions containing said resins |
| FR2746803A1 (en) * | 1996-03-29 | 1997-10-03 | Ceca Sa | PHENOL / DIENE NOVOLATE RESINS, PREPARATION METHOD AND RUBBER COMPOSITIONS COMPRISING SAID RESINS |
| US6265490B1 (en) | 1996-03-29 | 2001-07-24 | Ceca, S.A. | Phenol/diene novolac resins, process of preparation and rubber-based compositions containing the said resins |
| US7135539B2 (en) | 2000-09-08 | 2006-11-14 | Schenectady International Inc. | Novolac resins, process for preparing them and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0674321B2 (en) | 1994-09-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |