JPH1025343A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPH1025343A JPH1025343A JP8180445A JP18044596A JPH1025343A JP H1025343 A JPH1025343 A JP H1025343A JP 8180445 A JP8180445 A JP 8180445A JP 18044596 A JP18044596 A JP 18044596A JP H1025343 A JPH1025343 A JP H1025343A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- resin composition
- thermosetting resin
- phenolic hydroxyl
- reacting
- 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
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 15
- 239000011342 resin composition Substances 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 7
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229920003986 novolac Polymers 0.000 description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920003261 Durez Polymers 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- -1 isocyanate compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
(57)【要約】
【課題】 耐熱性を始め、種々の特性が優れ、硬化過程
において水やアンモニア等の縮合物が発生しない熱硬化
性樹脂組成物を提供する。
【解決手段】 ベンゾオキサジン環を２個以上有する化
合物とフェノール性水酸基と反応しうる官能基を有する
化合物とからなることを特徴とする熱硬化性樹脂組成物
であり、両化合物を溶融混合することが好ましい。PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which is excellent in various properties including heat resistance and does not generate condensates such as water and ammonia in a curing process. A thermosetting resin composition comprising a compound having two or more benzoxazine rings and a compound having a functional group capable of reacting with a phenolic hydroxyl group, wherein both compounds are melt-mixed. Is preferred.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、優れた流動性を有
し、貯蔵安定性に優れ、かつ耐熱性をはじめ種々の特性
において優れている新規な熱硬化性樹脂組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermosetting resin composition having excellent fluidity, excellent storage stability, and excellent properties such as heat resistance.
【０００２】[0002]
【従来の技術】代表的な熱硬化性樹脂の一つであるフェ
ノール樹脂は耐熱性、機械的性質、耐薬品性、電気絶縁
性等に優れており、かつ安価であるため、電気・電子部
品、車両部品、厨房器具等の成形材料、印刷回路用銅張
積層板、化粧板等の積層品、あるいは摩擦材、砥石、耐
火材、塗料、接着剤等の工業材料として広く用いられて
いる。しかし、その用途拡大にともない、さらなる高性
能化、高付加価値化に加えて、新しい硬化システムの開
発が望まれている。2. Description of the Related Art Phenolic resin, which is one of the typical thermosetting resins, is excellent in heat resistance, mechanical properties, chemical resistance, electrical insulation, etc. and is inexpensive, so it is used for electric and electronic parts. It is widely used as a molding material for vehicle parts, kitchen utensils and the like, a laminated product such as a copper-clad laminate for a printed circuit, a decorative board, and an industrial material such as a friction material, a grindstone, a refractory material, a paint, and an adhesive. However, with the expansion of applications, development of a new curing system in addition to higher performance and higher added value is desired.
【０００３】一般的なフェノール樹脂はフェノール類と
ホルムアルデヒド類との反応により生成される。すなわ
ち、酸性条件下反応させるとノボラックといわれるフェ
ノール核がメチレン基でつながったオリゴマーが得られ
る。このノボラックは可溶であるが硬化剤としてヘキサ
メチレンテトラミンと混合し加熱することにより硬化す
る。一方、塩基性条件下反応させるとレゾールと呼ばれ
るヒドロキシメチル基が置換したフェノール核がメチレ
ン結合でつなっがたオリゴマーが得られる。このレゾー
ルはノボラックとは異なり、ヒドロキシメチル基を有す
るので硬化剤を加えなくても加熱するだけで、ヒドロキ
シメチル基の縮合が起こり硬化する。[0003] General phenolic resins are formed by the reaction of phenols with formaldehydes. That is, when reacted under acidic conditions, an oligomer in which phenol nuclei called novolaks are connected by methylene groups is obtained. This novolak is soluble but is cured by mixing with hexamethylenetetramine as a curing agent and heating. On the other hand, when the reaction is carried out under basic conditions, an oligomer called a resole in which a phenol nucleus substituted with a hydroxymethyl group is connected by a methylene bond is obtained. Unlike the novolak, this resol has a hydroxymethyl group, so that the condensation of the hydroxymethyl group occurs and is cured only by heating without adding a curing agent.
【０００４】[0004]
【発明が解決しようとする課題】しかし、いずれの硬化
機構も硬化反応にともない、ヘキサメチレンテトラミン
の分解に起因するアンモニアガスや縮合反応に起因する
水蒸気が発生し、また、未反応フェノールやホルマリン
に起因する悪臭のため、作業環境の悪化や製品中のボイ
ド発生が問題となることがあった。However, in any curing mechanism, ammonia gas resulting from the decomposition of hexamethylenetetramine and water vapor resulting from the condensation reaction are generated along with the curing reaction, and unreacted phenol and formalin are produced. Due to the bad smell, the working environment may be degraded or voids may occur in the product.
【０００５】そこで、本発明らは、ベンゾオキサジン環
を有する化合物とエポキシ基、イソシアネート基、ある
いはベンゾオキサゾリンなどのようにフェノール性水酸
基と反応しうる官能基を有する化合物との配合物を、加
熱して反応させることにより、上記欠点が克服され、さ
らに優れた流動性を有し、貯蔵安定性に優れ、かつ優れ
た耐熱性、機械的性質及び電気特性を有する新規な熱硬
化性樹脂組成物を得ることができたものである。Accordingly, the present invention provides a method of heating a blend of a compound having a benzoxazine ring and a compound having a functional group capable of reacting with a phenolic hydroxyl group such as an epoxy group, an isocyanate group, or a benzoxazoline. The above-mentioned drawbacks are overcome by reacting with each other, and a novel thermosetting resin composition having excellent fluidity, excellent storage stability, and excellent heat resistance, mechanical properties and electrical properties is provided. That is what we could get.
【０００６】[0006]
【課題を解決するための手段】本発明は、ベンゾオキサ
ジン環を２個以上有する化合物と、エポキシ基、イソシ
アネート基あるいはベンソオキサゾリンなどのようにフ
ェノール性水酸基と反応しうる官能基を有する化合物と
からなることを特徴とする熱硬化性樹脂組成物、に関す
るものである。The present invention relates to a compound having two or more benzoxazine rings and a compound having a functional group capable of reacting with a phenolic hydroxyl group such as an epoxy group, an isocyanate group or a benzoxazoline. And a thermosetting resin composition comprising:
【０００７】ベンゾオキサジン環は下記に示す化学構造
を有する基であり、加熱により始めて開環し、フェノー
ル性水酸基と第３級アミンが同時に生成する。[0007] The benzoxazine ring is a group having the chemical structure shown below. The ring is opened only by heating, and a phenolic hydroxyl group and a tertiary amine are simultaneously formed.
【０００８】[0008]
【化２】 Embedded image
【０００９】例えば、式１に示すように、ベンゾオキサ
ジン環含有化合物の代表的なタイプである化合物Ａは、
加熱により反応して化合物Ｂあるいは化合物Ｃ等のフェ
ノール性水酸基と第３級アミンとを有する化合物が生成
する。For example, as shown in Formula 1, compound A, which is a typical type of benzoxazine ring-containing compound, is
Reaction by heating produces a compound having a phenolic hydroxyl group and a tertiary amine, such as compound B or compound C.
【００１０】[0010]
【化３】 Embedded image
【００１１】この生成した化合物は、エポキシ基、イソ
シアネート基あるいはベンゾオキサゾリンなどの、フェ
ノール性水酸基と反応しうる官能基を有する化合物と反
応し硬化して、強固な三次元構造を有する硬化物を与え
る。The resulting compound reacts with a compound having a functional group capable of reacting with a phenolic hydroxyl group, such as an epoxy group, an isocyanate group or a benzoxazoline, and cures to give a cured product having a strong three-dimensional structure. .
【００１２】[0012]
【発明の実施の形態】ベンゾオキサジン環を２個以上有
する化合物としては、上記化合物Ａの他に、化合物Ａの
ベンゾオキサジン環が一部開環重合したもの、あるいは
ベンゾオキサジン環を３個あるいは４個以上有するもの
も含まれることは当然である。BEST MODE FOR CARRYING OUT THE INVENTION As a compound having two or more benzoxazine rings, in addition to the above-mentioned compound A, a compound in which the benzoxazine ring of compound A is partially ring-opened polymerized, or a compound having three or four benzoxazine rings. Needless to say, those having more than one are also included.
【００１３】次に、フェノール性水酸基と反応しうる官
能基を有する化合物について説明する。フェノール性水
酸基と反応しうる官能基としては、特に限定するもので
はないが、エポキシ基、イソシアネート基あるいはベン
ソオキサゾリンなどが代表的なものである。本発明にお
いては、かかるフェノール性水酸基と反応しうる官能基
を少なくとも１個以上、好ましくは２個以上有する化合
物を、本発明の組成物の一方の化合物として配合する。Next, a compound having a functional group capable of reacting with a phenolic hydroxyl group will be described. The functional group capable of reacting with the phenolic hydroxyl group is not particularly limited, but is typically an epoxy group, an isocyanate group, or benzoxazoline. In the present invention, a compound having at least one, preferably two or more functional groups capable of reacting with the phenolic hydroxyl group is blended as one compound of the composition of the present invention.
【００１４】具体的には、例えば下記の化合物を挙げる
ことが出来る。即ち、ビスフェノールＡ型又はＦ型エポ
キシ樹脂、ノボラック型エポキシ樹脂等のエポキシ樹
脂、トリレンジイソシアネート、ジフェニレンメタンジ
イソシアネート等のイソシアネート化合物、あるいはこ
れらとポリオールとのプレポリマー、あるいはベンゾオ
キサゾリン化合物等である。Specifically, for example, the following compounds can be mentioned. That is, epoxy resins such as bisphenol A type or F type epoxy resin and novolak type epoxy resin, isocyanate compounds such as tolylene diisocyanate and diphenylenemethane diisocyanate, prepolymers of these with polyols, and benzoxazoline compounds.
【００１５】本発明の熱硬化性樹脂組成物において、硬
化機構はベンゾオキサジン環の開環による重合と、生成
したフェノール性水酸基とこのフェノール性水酸基と反
応しうる官能基との付加反応である。このため、硬化過
程において水やアンモニア等の縮合物が発生しない。し
かも、ベンゾオキサジン環は体積膨張しながら開環する
ために、フェノール樹脂の一般的な硬化反応に伴う硬化
収縮を抑えることができる。In the thermosetting resin composition of the present invention, the curing mechanism is polymerization by ring-opening of a benzoxazine ring, and addition reaction between a formed phenolic hydroxyl group and a functional group capable of reacting with the phenolic hydroxyl group. For this reason, condensates such as water and ammonia do not occur during the curing process. In addition, since the benzoxazine ring opens while expanding in volume, it is possible to suppress curing shrinkage due to a general curing reaction of the phenol resin.
【００１６】ベンゾオキサジン環を有する化合物とフェ
ノール性水酸基と反応しうる官能基を有する化合物と
は、常温では実質的に反応しない。更に、ベンゾオキサ
ジン環が開環した場合でもフェノール性水酸基と反応し
うる官能基を有する化合物とは、常温では実質的に反応
しない。従って、両化合物を単に混合した場合はもちろ
んのこと、加熱溶融混合した場合でも、常温において長
期間保存することが出来る。更に、本発明の組成物にお
いて、ベンゾオキサジン環がすでに開環している場合で
も、同様に常温において長期間保存することが出来る。The compound having a benzoxazine ring and the compound having a functional group capable of reacting with a phenolic hydroxyl group do not substantially react at room temperature. Furthermore, even when the benzoxazine ring is opened, it does not substantially react with a compound having a functional group that can react with a phenolic hydroxyl group at room temperature. Therefore, not only when both compounds are simply mixed but also when they are melted and mixed by heating, they can be stored at room temperature for a long period of time. Further, in the composition of the present invention, even when the benzoxazine ring is already opened, it can be similarly stored at room temperature for a long period of time.
【００１７】[0017]
【実施例】以下に実施例及び比較例により本発明を説明
する。The present invention will be described below with reference to examples and comparative examples.
【００１８】合成例 ベンゾオキサジン環を有するビス
フェノールＡ（Ｂ−ａ）の合成 還流冷却器、温度計および滴下漏斗を備えた１Ｌのナス
フラスコに２．４ｍｏｌのホルムアルデヒド水溶液、１
６０ｍｌのジオキサンを加え、氷冷しながら１．２ｍｏ
ｌのアニリン（４０ｍｌのジオキサン溶液）を徐々に添
加し、１０℃以下にて１０分間攪拌した。０．６ｍｏｌ
のビスフェノールＡ（２００ｍｌのジオキサン溶液）を
加え、環流条件で６時間攪拌し、反応させた。溶媒を除
去した後、生成物をエチルエーテルで抽出、蒸留水およ
び３ＮのＮａＯＨで数回洗浄した。無水ＭｇＳＯ4 で乾
燥した後、減圧乾燥して、所望の化合物Ｂ−ａを得た。
化学反応式を式２に示す。 Synthesis Example Bis having a benzoxazine ring
Synthesis of Phenol A ( Ba) A 2.4 mol formaldehyde aqueous solution was placed in a 1 L eggplant flask equipped with a reflux condenser, a thermometer and a dropping funnel.
Add 60 ml of dioxane, and cool with ice
l of aniline (40 ml of dioxane solution) was gradually added, and the mixture was stirred at 10 ° C. or lower for 10 minutes. 0.6mol
Of bisphenol A (200 ml of dioxane solution) was added thereto, and the mixture was stirred and reacted at reflux for 6 hours. After removing the solvent, the product was extracted with ethyl ether and washed several times with distilled water and 3N NaOH. After drying over anhydrous MgSO 4 , it was dried under reduced pressure to obtain the desired compound Ba.
Formula 2 shows the chemical reaction formula.
【００１９】[0019]
【化４】 Embedded image
【００２０】実施例 Ｂ−ａとエポキシ樹脂（ＤＧＥＢ
Ａ）との反応による硬化 エポキシ樹脂ＤＧＥＢＡと化合物Ｂ−ａとを等モル配合
し、１２０℃にて溶融混合し、シリコンゴム製の型に注
型した。その後、１５０℃,１時間、１７０℃,１時間、
１９０℃,２時間、２００℃,２時間、更に２２０℃,２
時間加熱して、硬化させた。化学反応式を式３に示す。 Example Ba and an epoxy resin (DGEB
The cured epoxy resin DGEBA cured by the reaction with A) and the compound Ba were mixed in an equimolar amount, melt-mixed at 120 ° C., and cast into a silicone rubber mold. After that, 150 ° C, 1 hour, 170 ° C, 1 hour,
190 ° C, 2 hours, 200 ° C, 2 hours, 220 ° C, 2 hours
Heat for an hour to cure. Formula 3 shows the chemical reaction formula.
【００２１】[0021]
【化５】 Embedded image
【００２２】比較例 ビスフェノールＡ型ノボラック
（ＢｉｓＡ−Ｎ）とエポキシ樹脂（ＤＧＥＢＡ）との反
応による硬化 エポキシ樹脂ＤＧＥＢＡとＢｉｓＡ−Ｎとを等モル配合
し、１００℃にて溶融混合した後、触媒として２−エチ
ル−４−メチルイミダゾールを加えて速やかにシリコン
ゴム製の型に注型した。１００℃で２時間加熱して初期
硬化した後、１５０℃,１時間、１７０℃,１時間、１９
０℃,２時間、２００℃,２時間、更に２２０℃,２時間
加熱して、硬化させた。化学反応式を式４に示す。 Comparative Example Bisphenol A type novolak
(BisA-N) and epoxy resin (DGEBA)
After equimolar blending of the cured epoxy resin DGEBA and Bis-A-N, melt-mixing at 100 ° C., 2-ethyl-4-methylimidazole was added as a catalyst, and the mixture was immediately cast into a silicone rubber mold. . After initial curing by heating at 100 ° C. for 2 hours, 150 ° C., 1 hour, 170 ° C., 1 hour, 19
It was cured by heating at 0 ° C. for 2 hours, 200 ° C. for 2 hours, and further 220 ° C. for 2 hours. Formula 4 shows the chemical reaction formula.
【００２３】[0023]
【化６】 Embedded image
【００２４】表１に、実施例及び比較例において得られ
た樹脂硬化物の特性を示す。Table 1 shows the properties of the cured resin products obtained in Examples and Comparative Examples.
【００２５】[0025]
【表１】 [Table 1]
【００２６】（測定方法） １．ガラス転移温度：動的粘弾性測定のｔａｎδのピー
ク温度 ２．臨界応用拡大係数：ＡＳＴＭ Ｄ ５０４５に従い三
点曲げ法にて測定した。 ３．体積抵抗率：ＪＩＳ Ｃ ６４８１により測定した。 ４．吸水率：大きさ５０mmφ×３mm厚の注型品を２時間
煮沸し、重量変化から求めた。(Measurement method) 1. Glass transition temperature: peak temperature of tan δ in dynamic viscoelasticity measurement Critical application magnification factor: Measured by a three-point bending method according to ASTM D 5045. 3. Volume resistivity: Measured according to JIS C6481. 4. Water absorption: A cast product having a size of 50 mmφ × 3 mm thick was boiled for 2 hours and determined from a change in weight.
【００２７】[0027]
【発明の効果】本発明の熱硬化性樹脂組成物において、
その硬化機構は前述のごとく開環重合と付加反応とであ
るため、硬化過程において水やアンモニア等の縮合物が
発生せず、かつ体積膨張しながら開環するために、フェ
ノール樹脂の一般的な硬化反応に伴う硬化収縮を抑える
ことができる。そして、優れた流動性を有し、貯蔵安定
性に優れ、かつ耐熱性をはじめ機械的特性や電気特性な
ど種々の特性において優れている。従って、本発明の熱
硬化性樹脂組成物は、成形材料、注型品、接着剤、塗料
等として幅広い分野での応用が可能である。According to the thermosetting resin composition of the present invention,
Since the curing mechanism is a ring-opening polymerization and an addition reaction as described above, a condensate such as water or ammonia is not generated in the curing process, and the ring is opened while expanding in volume. Curing shrinkage accompanying the curing reaction can be suppressed. And it has excellent fluidity, excellent storage stability, and is excellent in various properties such as heat resistance, mechanical properties and electrical properties. Therefore, the thermosetting resin composition of the present invention can be applied in a wide range of fields as molding materials, cast products, adhesives, paints, and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大塚 恵子 大阪府豊中市本町５丁目10番３−304号 (72)発明者 福田 明徳 奈良県生駒市新生駒台６番21号 (72)発明者 炭山 宜也 東京都品川区東品川２丁目５番８号 住友 デュレズ株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keiko Otsuka 5-10-3-304, Honcho, Toyonaka City, Osaka (72) Inventor Akinori Fukuda 6-21, Shinsei Komadai, Ikoma City, Nara Prefecture (72) Inventor Yoshiya Sumiya 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Durez Co., Ltd.
Claims (5)
合物とフェノール性水酸基と反応しうる官能基を有する
化合物とからなることを特徴とする熱硬化性樹脂組成
物。1. A thermosetting resin composition comprising a compound having two or more benzoxazine rings and a compound having a functional group capable of reacting with a phenolic hydroxyl group.
合物とフェノール性水酸基と反応しうる官能基を有する
化合物とを溶融混合してなる請求項１記載の熱硬化性樹
脂組成物。2. The thermosetting resin composition according to claim 1, wherein a compound having two or more benzoxazine rings and a compound having a functional group capable of reacting with a phenolic hydroxyl group are melt-mixed.
合物が、下記化学式で表されるものである請求項１又は
２記載の熱硬化性樹脂組成物。 【化１】 3. The thermosetting resin composition according to claim 1, wherein the compound having two or more benzoxazine rings is represented by the following chemical formula. Embedded image
が、エポキシ基、イソシアネート基あるいはベンゾオキ
サゾリンである請求項１、２又は３記載の熱硬化性樹脂
組成物。4. The thermosetting resin composition according to claim 1, wherein the functional group capable of reacting with the phenolic hydroxyl group is an epoxy group, an isocyanate group or a benzoxazoline.
合物の一部に代えて、ベンゾオキサジン環が開環してい
る化合物が使用されてなる請求項１、２、３又は４記載
の熱硬化性樹脂組成物。5. The thermosetting composition according to claim 1, wherein a compound having an open benzoxazine ring is used instead of a part of the compound having two or more benzoxazine rings. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8180445A JPH1025343A (en) | 1996-07-10 | 1996-07-10 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8180445A JPH1025343A (en) | 1996-07-10 | 1996-07-10 | Thermosetting resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1025343A true JPH1025343A (en) | 1998-01-27 |
Family
ID=16083365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8180445A Pending JPH1025343A (en) | 1996-07-10 | 1996-07-10 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1025343A (en) |
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|---|---|---|---|---|
| WO1999042523A1 (en) * | 1998-02-23 | 1999-08-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermosetting polyphenylene ether resin composition, cured resin composition obtained therefrom, and laminated structure |
| JP2003064155A (en) * | 2001-08-23 | 2003-03-05 | Nippon Steel Chem Co Ltd | Thermosetting resin composition |
| JP2010001481A (en) * | 2005-09-03 | 2010-01-07 | Samsung Sdi Co Ltd | Polybenzoxazine-based compound |
| JP2010150364A (en) * | 2008-12-25 | 2010-07-08 | Akebono Brake Ind Co Ltd | Binder resin composition for friction material and friction material for brake |
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-
1996
- 1996-07-10 JP JP8180445A patent/JPH1025343A/en active Pending
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