JPH0580945B2 - - Google Patents
Info
- Publication number
- JPH0580945B2 JPH0580945B2 JP61232964A JP23296486A JPH0580945B2 JP H0580945 B2 JPH0580945 B2 JP H0580945B2 JP 61232964 A JP61232964 A JP 61232964A JP 23296486 A JP23296486 A JP 23296486A JP H0580945 B2 JPH0580945 B2 JP H0580945B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- resin
- epoxy resin
- resin composition
- glycidyl
- 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
- 239000011342 resin composition Substances 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims description 21
- 229920001187 thermosetting polymer Polymers 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 5
- 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 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 4
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- -1 glycidyl ester Chemical class 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 2
- CRSDMXKCMBHKCS-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)phenyl]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1CC1CO1 CRSDMXKCMBHKCS-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 claims 1
- 150000004992 toluidines Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 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 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 239000003365 glass fiber Substances 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
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
〔技術分野〕
本発明は、特定の熱硬化性樹脂と特定の熱可塑
性樹脂とを均一に含み、熱硬化性樹脂の優れた機
械的特性及び熱的特性と熱可塑性樹脂の優れた靭
性（タフネス）とを兼ね備えた成形物を与える樹
脂組成物に関する。
〔従来技術及び問題点〕
近年、熱硬化性樹脂の成形物及びこの熱硬化性
樹脂をマトリツクスとする複合材料は、優れた寸
法安定性、耐熱性、機械的特性、耐薬品性、耐候
性等を与えることから、広く一般産業、電気分野
等に利用されてきた。
この反面、熱硬化性樹脂成形物は、樹脂の伸度
が低く、脆いために、靭性、耐衝撃性に劣ること
が指摘され、その改善が求められていた。
熱硬化性樹脂の成形物等の靭性及び耐衝撃性を
改善する手段としては、熱硬化性樹脂にゴム成分
を混合する方法、熱可塑性樹脂成分を混合する方
法、充填剤を混合する方法等が考えられてきた。
しかしながら、熱硬化性樹脂にゴム成分を混合
する方法の場合、成形物等の靭性及び耐衝撃性は
改善されるが、耐熱性及び機械的特性が低下する
ためその配合量は規制され、用途によつては低配
合量に留まり、充分な改質効果は得られていな
い。また、熱硬化性樹脂に熱可塑性樹脂を混合す
る方法の場合、微粉末状で入れたり、溶剤に熱可
塑性樹脂を溶解させた後に熱硬化性樹脂を加える
手段が採られていたが、微粉末で入れたときは、
不均一な組成物となり、機械的性質が低下する傾
向があつた。また、溶剤を用いて混合させるとき
は、混合後の脱溶剤に問題があつたり、その調製
法が面倒であつたり、微量の残存溶剤が耐熱性を
低下させる等の欠点を有していた。
〔発明の目的〕
本発明の目的は、上記の如き問題点を克服し、
均一で且つ簡単に熱硬化性樹脂／熱可塑性樹脂の
混合物を無溶剤で調製することができ、優れた耐
熱性及び靭性・衝撃強さ等の機械的特性を成形物
に与える樹脂組成物を提供することにある。
〔発明の構成及び効果〕
本発明は、〔Ａ〕成分としてエポキシ樹脂と
〔Ｂ〕成分としてポリカーボネート、ポリスルホ
ン、ポリエーテルスルホン、ポリエーテルイミド
の１種又は２種以上の熱可塑性樹脂と〔Ｃ〕成分
として該熱可塑性樹脂溶解能を有する前記熱硬化
性樹脂以外のエポキシ樹脂及び／又はエポキシ基
を有する反応性希釈剤とを含み、且つ〔Ａ〕、
〔Ｂ〕、〔Ｃ〕の各成分の比がそれぞれ、１〜96重
量％、２〜50重量％、２〜49重量％であることを
特徴とする樹脂組成物である。本発明の樹脂組成
物では、〔Ｃ〕成分が、〔Ｂ〕成分を溶解せしめ、
〔Ｃ〕成分が〔Ａ〕成分と〔Ｂ〕成分の媒介とし
て働くため、調製法が容易で、しかも無溶剤で均
一な熱硬化性樹脂成分／熱可塑性樹脂成分の混合
物を与えることができる。従つて、それから得ら
れる成形物も、熱硬化性樹脂成分の優れた機械的
特性、耐熱性を保有しながら、靭性及びそれらに
伴なう耐衝撃性が著しく改善されている。
本発明において〔Ａ〕成分のエポキシ樹脂に
は、ビスフエノールＡ型エポキシ樹脂（例えば、
シエル化学社製エピコート828）、フエノール・ノ
ボラツク型エポキシ樹脂（例えば、チバ、ガイギ
ー社製EPN1138）、クレゾール・ノボラツク型エ
ポキシ樹脂（例えば、日本化薬（株）社製
EOCN102）、グリシジルアミン型エポキシ樹脂
（例えば、チバ・ガイギー社製アラルダイト
MY720）があり、これらを単独又は２種以上組
合せて使用する。
本発明において〔Ｂ〕成分の熱可塑性樹脂とし
ては、ポリカーボネート、ボリスルホン、ポリエ
ーテルスルホン、ポリエーテルイミドである。こ
れらの熱可塑性樹脂は２種以上組合せて使用する
こともできる。
これらの熱可塑性樹脂〔Ｂ〕成分は、粒子径
400μｍ以下、特に100μｍ以下の粉末状であるこ
とが好ましい。また、耐熱性の点でガラス転移温
度が100℃以上のものが好ましい。
本発明において〔Ｃ〕成分のうち熱可塑性樹脂
溶解能を有するエポキシ樹脂としては、グリシジ
ルエステル型エポキシ樹脂（例えば、シエル化学
社製エピコートGEE）、グリシジルアミン型エポ
キシ樹脂（例えば、日本化薬（株）社製GOT、
GAN）であり、これらのエポキシ樹脂は〔Ａ〕
成分として配合されたエポキシ樹脂以外のエポキ
シ樹脂である。
〔Ｃ〕成分の熱可塑性樹脂溶解能を有する反応
性希釈剤のうち、ジエポキシ化合物としては、ジ
グリシジルエーテル、ブタンジオールジグリシジ
ルエーテル、２−グリシジルフエニルグリシジル
エーテル、レゾルシノールジグリシジルエーテル
等があり、モノエポキシ化合物としては、アルキ
ルフエノールグリシジルエーテル、フエニルグリ
シジルエーテル、ブチルグリシジルエーテル、ク
レゾールグリシジルエーテル等がある。
これら〔Ｃ〕成分は２種以上組合せて使用する
こともできる。また、25℃の粘度が150ポイズ以
下のものを用いることが好ましい。
〔Ｂ〕成分と〔Ｃ〕成分との組合せは、〔Ｃ〕
成分が〔Ｂ〕成分を溶解する関係にあることが必
要であり、このような関係にない場合は、樹脂組
成物が均一とならず、本発明の目的を達成するこ
とができない。
〔Ｂ〕成分と相溶性のある〔Ｃ〕成分との組合
せを示すと、下記の通りである。
[Technical field] The present invention uniformly contains a specific thermosetting resin and a specific thermoplastic resin, and has excellent mechanical properties and thermal properties of the thermosetting resin, and excellent toughness (toughness) of the thermoplastic resin. ) It relates to a resin composition that provides a molded article having the following properties. [Prior art and problems] In recent years, thermosetting resin molded products and composite materials using this thermosetting resin as a matrix have been developed with excellent dimensional stability, heat resistance, mechanical properties, chemical resistance, weather resistance, etc. It has been widely used in general industry, electrical fields, etc. because of its ability to provide On the other hand, it has been pointed out that thermosetting resin molded products have poor toughness and impact resistance because the resin has low elongation and is brittle, and improvements have been sought. Methods for improving the toughness and impact resistance of thermosetting resin molded articles include methods of mixing a rubber component with a thermosetting resin, a method of mixing a thermoplastic resin component, a method of mixing a filler, etc. has been considered. However, in the case of a method of mixing a rubber component with a thermosetting resin, the toughness and impact resistance of molded products are improved, but the amount of the mixture is regulated because the heat resistance and mechanical properties are reduced. In the end, the blending amount remains low, and a sufficient modifying effect is not obtained. In addition, in the case of a method of mixing a thermoplastic resin with a thermosetting resin, the methods of adding the thermosetting resin in the form of a fine powder or adding the thermosetting resin after dissolving the thermoplastic resin in a solvent have been adopted. When you enter it with
There was a tendency for the composition to be non-uniform and for mechanical properties to deteriorate. In addition, when mixing using a solvent, there are problems in removing the solvent after mixing, the preparation method is troublesome, and a small amount of residual solvent reduces heat resistance. [Object of the invention] The object of the present invention is to overcome the above-mentioned problems,
To provide a resin composition that can uniformly and easily prepare a mixture of thermosetting resin/thermoplastic resin without using a solvent, and that provides molded products with excellent mechanical properties such as heat resistance, toughness, and impact strength. It's about doing. [Structure and effects of the invention] The present invention comprises an epoxy resin as the component [A], one or more thermoplastic resins selected from polycarbonate, polysulfone, polyethersulfone, and polyetherimide as the component [B], and [C] [A], which contains as a component an epoxy resin other than the thermosetting resin having the ability to dissolve the thermoplastic resin and/or a reactive diluent having an epoxy group;
The resin composition is characterized in that the ratios of the components [B] and [C] are 1 to 96% by weight, 2 to 50% by weight, and 2 to 49% by weight, respectively. In the resin composition of the present invention, the [C] component dissolves the [B] component,
Since the [C] component acts as a mediator between the [A] component and the [B] component, the preparation method is easy, and a uniform thermosetting resin component/thermoplastic resin component mixture can be obtained without using a solvent. Therefore, the molded product obtained therefrom retains the excellent mechanical properties and heat resistance of the thermosetting resin component, while having significantly improved toughness and impact resistance associated therewith. In the present invention, the epoxy resin of component [A] includes bisphenol A-type epoxy resin (for example,
Epikote 828 (manufactured by Ciel Kagaku Co., Ltd.), phenol novolac type epoxy resin (e.g. Ciba, EPN1138 manufactured by Geigy), cresol novolak type epoxy resin (e.g. manufactured by Nippon Kayaku Co., Ltd.)
EOCN102), glycidylamine type epoxy resin (e.g. Araldite manufactured by Ciba Geigy)
MY720), and these can be used alone or in combination of two or more. In the present invention, the thermoplastic resin of component [B] includes polycarbonate, boris sulfone, polyether sulfone, and polyetherimide. Two or more of these thermoplastic resins can also be used in combination. These thermoplastic resin [B] components have a particle size of
It is preferably in powder form with a diameter of 400 μm or less, particularly 100 μm or less. Further, from the viewpoint of heat resistance, those having a glass transition temperature of 100° C. or higher are preferable. In the present invention, as the epoxy resin having a thermoplastic resin dissolving ability among component [C], glycidyl ester type epoxy resin (for example, Epicoat GEE manufactured by Ciel Chemical Co., Ltd.), glycidyl amine type epoxy resin (for example, Nippon Kayaku Co., Ltd. ) company GOT,
GAN), and these epoxy resins are [A]
This is an epoxy resin other than the epoxy resin blended as a component. [C] Among the reactive diluents having thermoplastic resin dissolving ability, diepoxy compounds include diglycidyl ether, butanediol diglycidyl ether, 2-glycidyl phenyl glycidyl ether, resorcinol diglycidyl ether, etc. Examples of monoepoxy compounds include alkylphenol glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, and cresol glycidyl ether. These [C] components can also be used in combination of two or more. Further, it is preferable to use one having a viscosity of 150 poise or less at 25°C. The combination of [B] component and [C] component is [C]
It is necessary that the components are in a relationship to dissolve component [B], and if such a relationship is not present, the resin composition will not be uniform and the object of the present invention cannot be achieved. Combinations of component [B] and component [C] that are compatible are as follows.
【表】
〔Ａ〕成分／〔Ｂ〕成分／〔Ｃ〕成分の組合せ
において、調製方法を簡単にするため、〔Ｂ〕成
分を予め〔Ｃ〕成分に溶解させ、その後に〔Ａ〕
成分を加えるという方法を採ることが好ましい。
〔Ａ〕成分／〔Ｂ〕成分／〔Ｃ〕成分の配合比
は、〔Ａ〕、〔Ｂ〕、〔Ｃ〕がそれぞれ、１〜96重量
％、２〜50重量％、２〜49重量％である。
〔Ａ〕成分が所定の範囲外であると本発明の目
的は達成されない。〔Ｂ〕成分の配合量が50重量
％超の場合は溶融粘度が高くなり、このため混
合、繊維間への含浸が成形が困難となり、良好な
成形物が得られ難い。〔Ｃ〕成分の配合量が49重
量％超の場合、樹脂組成物の耐熱性が極端に低下
し、また、機械的性質も低くなり好ましくない。
〔Ｂ〕成分、〔Ｃ〕成分がそれぞれ２重量％未満で
は、本発明の目的は達成されない。〔Ｂ〕成分／
〔Ｃ〕成分の重量比は２以下とするのがよい。比
が２超の場合、組成物の粘度が上昇し取扱性が悪
く、プリプレグとするとき繊維間への含浸性が低
下しタツクも低くなり好ましくない。また、機械
的特性の低下を招来する。〔Ｃ〕成分の配合量は
〔Ｂ〕成分の配合量との関係で樹脂組成物が均一
組成となる最小限に留めるのが好ましい。
本発明の樹脂組成物は、上記の各必須成分以外
に、それぞれの目的、用途、使用条件によつて、
強化材料、例えばガラス繊維、炭素繊維、芳香族
ポリアミド繊維、金属繊維等を加えることもでき
る。また、ブタジエン−アクリロニトリルゴムの
ような重合強化材、三酸化アンチモンのような難
燃剤、シリカ粉末等の充填材、着色材等を添加す
ることもできる。また、用いる樹脂の種類によ
り、架橋反応の開始剤、硬化剤、硬化促進剤を必
要とするもの、或いは必要としないものがあり、
これらは必要に応じ適宜選択される。
本発明の樹脂組成物の調製は、例えば以下の方
法により行うことができる。
即ち、各成分を混練装置に供給し、好ましく
は、不活性ガス雰囲気下、加熱混練する。この際
の加熱温度は熱硬化性樹脂の硬化開始温度より低
温とする。
或いは、〔Ｂ〕成分に〔Ｃ〕成分を溶解した後
に〔Ａ〕成分及び必要により硬化剤等を加え混練
する。
通常は20〜200℃の温度、特に好ましくは50〜
150℃の温度にて調製する。
本発明の樹脂組成物を強化材繊維に含浸させプ
リプレグとする場合は、既に知られている、所謂
ホツトメルト法により行うことができる。また、
本発明の樹脂組成物を成形させる方法として、加
熱硬化、UV（紫外線）硬化、EB（電子線）硬化、
水分による硬化等があるが、その方法及び硬化手
段の組合せは、熱硬化性樹脂の種類により選択で
きる。
本発明の樹脂組成は、〔Ａ〕成分の熱硬化性樹
脂と〔Ｂ〕成分の熱可塑性樹脂の媒介として
〔Ｃ〕成分が介在するため、各成分が均一に混合
された樹脂組成物となり、しかも、残存溶剤の影
響もなく、熱硬化性樹脂の優れた耐熱性と熱可塑
性樹脂の靭性・衝撃強さ等を兼ね備えた優れた樹
脂組成物である。
また、溶解性の問題から、〔Ｂ〕成分と〔Ｃ〕
成分の均一混合物を〔Ａ〕成分に混合したとき、
〔Ｂ〕成分が或る大きさの相となつて析出してく
る場合もあるが、その場合でも単純に〔Ａ〕成分
と〔Ｂ〕成分を混合したときより、混合状態がよ
り均一であることはいうまでもない。
このものは、単独成形物にて或いは繊維強化材
との複合材料成形物にて電気分野、医療分野、宇
宙航空分野、土木・建築分野、一般産業分野等で
広く使用することができる。
〔実施例及び比較例〕
以下、本発明を実施例により説明するとともに
比較例を示す。
実施例１〜６及び比較例１〜７
〔Ａ〕成分としてエポキシ樹脂を用い、〔Ａ〕、
〔Ｂ〕、〔Ｃ〕成分が、第２表に示す種類及び配合
割合になるよう計量してビーカーに取つた。これ
を、110℃、１時間攪拌しながら加熱させ、均一
な〔Ａ〕、〔Ｂ〕、〔Ｃ〕成分の混合物を得た。
さらに、ジアミノジフエニルスルホン等のエポ
キシ樹脂用硬化剤を加え、100℃、１時間加熱混
合し、熱硬化性樹脂組成物を得た。この組成物を
シリコーンゴム型に入れ、180℃、２時間加圧下
で硬化させ、樹脂組成物の硬化物を得た。
硬化物より試験片を切り出し、ガラス転移温度
の測定、破壊靭性試験及びアイゾツト衝撃試験を
行つた。得られた結果をまとめて第２表に示す。
また、比較例として、〔Ａ〕成分のみの系で、
かつ〔Ｂ〕、〔Ｃ〕成分を入れない系（比較例１〜
５）、〔Ａ〕、〔Ｃ〕成分のみの系（比較例６、７）
及び〔Ｂ〕成分の代りに宇部興産（株）社製ブタ
ジエン−アクリロニトリルゴムCTBN、
Hycar1300×13を入れた系（比較例７）について
も実施例と同条件で樹脂組成物を調製し、硬化物
を成形した後に物性を測定した。得られた結果を
第２表に示す。[Table] For the combination of [A] component / [B] component / [C] component, in order to simplify the preparation method, the [B] component is dissolved in the [C] component in advance, and then [A]
It is preferable to adopt a method of adding components. The blending ratio of [A] component/[B] component/[C] component is 1 to 96% by weight, 2 to 50% by weight, and 2 to 49% by weight for [A], [B], and [C], respectively. It is. If the [A] component is outside the predetermined range, the object of the present invention will not be achieved. When the blending amount of component [B] exceeds 50% by weight, the melt viscosity becomes high, making it difficult to mix and impregnate between the fibers, making it difficult to form a good molded product. If the blending amount of component [C] exceeds 49% by weight, the heat resistance of the resin composition will be extremely lowered, and the mechanical properties will also be lowered, which is not preferable.
If component [B] and component [C] are each less than 2% by weight, the object of the present invention cannot be achieved. [B] Component/
The weight ratio of component [C] is preferably 2 or less. If the ratio is more than 2, the viscosity of the composition increases, making it difficult to handle, and when used as a prepreg, the impregnation between fibers decreases and the tack becomes low, which is not preferable. It also causes a decrease in mechanical properties. It is preferable that the amount of component [C] blended is kept to a minimum so that the resin composition has a uniform composition in relation to the amount of component [B] blended. In addition to the above-mentioned essential components, the resin composition of the present invention may also include, depending on its purpose, use, and usage conditions.
Reinforcing materials such as glass fibers, carbon fibers, aromatic polyamide fibers, metal fibers, etc. can also be added. Further, polymer reinforcing materials such as butadiene-acrylonitrile rubber, flame retardants such as antimony trioxide, fillers such as silica powder, colorants, etc. can also be added. In addition, depending on the type of resin used, some require initiators, curing agents, and curing accelerators for crosslinking reactions, and others do not.
These are selected as appropriate. The resin composition of the present invention can be prepared, for example, by the following method. That is, each component is supplied to a kneading device, and preferably heated and kneaded under an inert gas atmosphere. The heating temperature at this time is lower than the curing start temperature of the thermosetting resin. Alternatively, after dissolving component [C] in component [B], component [A] and, if necessary, a curing agent and the like are added and kneaded. Usually the temperature is between 20 and 200℃, particularly preferably between 50 and
Prepare at a temperature of 150°C. When reinforcing fibers are impregnated with the resin composition of the present invention to form a prepreg, the so-called hot melt method, which is already known, can be used. Also,
Methods for molding the resin composition of the present invention include heat curing, UV (ultraviolet) curing, EB (electron beam) curing,
There is curing by moisture, etc., and the combination of the method and curing means can be selected depending on the type of thermosetting resin. In the resin composition of the present invention, since the component [C] is present as a mediator between the thermosetting resin of the component [A] and the thermoplastic resin of the component [B], the resin composition is a resin composition in which each component is uniformly mixed. Moreover, it is an excellent resin composition that is free from the influence of residual solvent and has both the excellent heat resistance of a thermosetting resin and the toughness, impact strength, etc. of a thermoplastic resin. Also, due to solubility issues, [B] component and [C]
When a homogeneous mixture of components is mixed with component [A],
[B] component may precipitate as a phase of a certain size, but even in that case, the mixed state is more uniform than when simply mixing [A] component and [B] component. Needless to say. This product can be widely used in the electrical field, medical field, aerospace field, civil engineering/architecture field, general industrial field, etc., either as a single molded product or as a composite material molded product with fiber reinforced material. [Examples and Comparative Examples] Hereinafter, the present invention will be explained with reference to Examples, and a Comparative Example will be shown. Examples 1 to 6 and Comparative Examples 1 to 7 [A] Using an epoxy resin as the component, [A],
Components [B] and [C] were weighed and placed in a beaker so that the types and blending ratios were as shown in Table 2. This was heated at 110° C. for 1 hour with stirring to obtain a homogeneous mixture of components [A], [B], and [C]. Furthermore, a curing agent for epoxy resin such as diaminodiphenylsulfone was added, and the mixture was heated and mixed at 100° C. for 1 hour to obtain a thermosetting resin composition. This composition was placed in a silicone rubber mold and cured under pressure at 180°C for 2 hours to obtain a cured resin composition. Test pieces were cut out from the cured product and subjected to measurement of glass transition temperature, fracture toughness test, and Izot impact test. The obtained results are summarized in Table 2. In addition, as a comparative example, in a system containing only the [A] component,
and [B], a system in which [C] components are not added (Comparative Examples 1~
5), [A], [C] component only system (Comparative Examples 6 and 7)
and [B] butadiene-acrylonitrile rubber CTBN manufactured by Ube Industries, Ltd. in place of component;
Regarding the system containing Hycar1300×13 (Comparative Example 7), a resin composition was prepared under the same conditions as in the example, and the physical properties were measured after molding the cured product. The results obtained are shown in Table 2.
【表】【table】
【表】
第２表によれば、実施例１〜６の場合は、比較
例１〜６に比べ、破壊靭性及びアイゾツト衝撃強
さに優れ、靭性に富むことがわかる。
また、比較例７の場合は、靭性に優れるが、耐
熱性の低下が著しいことがわかる。[Table] According to Table 2, it can be seen that Examples 1 to 6 have superior fracture toughness and Izot impact strength, and are rich in toughness, compared to Comparative Examples 1 to 6. Moreover, in the case of Comparative Example 7, although the toughness is excellent, the heat resistance is significantly deteriorated.
Claims (1)
分としてポリカーボネート、ポリスルホン、ポリ
エーテルスルホン、ポリエーテルイミドの１種又
は２種以上の熱可塑性樹脂と、〔Ｃ〕成分として
該熱可塑性樹脂溶解能を有する前記熱硬化性樹脂
以外のエポキシ樹脂及び／又はエポキシ基を有す
る反応性希釈剤とを含み、且つ〔Ａ〕、〔Ｂ〕、
〔Ｃ〕の各成分の比がそれぞれ、１〜96重量％、
２〜50重量％、２〜49重量％であることを特徴と
する樹脂組成物。 ２ 〔Ｃ〕成分の熱可塑性樹脂溶解能を有するエ
ポキシ樹脂が、粘度150ポイズ（温度25℃）以下
のグルシジルエステル型エポキシ樹脂及びグリシ
ジルアミン型エポキシ樹脂である特許請求の範囲
１項記載の樹脂組成物。 ３ 〔Ｃ〕成分のエポキシ基を有する反応性希釈
剤が、ジエポキシ化合物として、ジグリシジルエ
ーテル、ブタンジオールジグリシジルエーテル、
２−グリシジルフエニルグリシジルエーテル、レ
ゾルシノールジグリシジルエーテルであり、モノ
エポキシ化合物として、アルキルフエノールグリ
シジルエーテル、フエニルグリシジルエーテル、
ブチルグリシジルエーテル、クレゾールグリシジ
ルエーテル、である特許請求の範囲１項記載の樹
脂組成物。 ４ 〔Ｂ〕成分／〔Ｃ〕成分の重量比が、２以下
である特許請求の範囲１項記載の樹脂組成物。 ５ 〔Ｃ〕成分の熱可塑性樹脂溶解能を有するエ
ポキシ樹脂及び／又はエポキシ基を有する反応性
希釈剤が、ジグリシジルアニリン、ジグリシジル
トルイジン、ジグリシジルエーテル、フエニルグ
リシジルエーテル、クレゾールグリシジルエーテ
ルである特許請求の範囲１項記載の樹脂組成物。 ６ 〔Ｂ〕成分を〔Ｃ〕成分に溶解した後、〔Ａ〕
成分と混合することによつて調製された特許請求
の範囲１項記載の樹脂組成物。 のグリシジルエステル型エポキシ樹脂及びグリシ
ジルアミン型エポキシ樹脂である特許請求の範囲
１項記載の樹脂組成。 ７ 〔Ａ〕成分であるエポキシ樹脂の硬化剤とし
てジアミノジフエニルスルホン、ジシアンジアミ
ド、BF3・モノエチルアミンを含む特許請求の範
囲１記載の樹脂組成物。[Scope of Claims] 1. An epoxy resin as the [A] component, one or more thermoplastic resins selected from polycarbonate, polysulfone, polyethersulfone, and polyetherimide as the [B] component, and one or more thermoplastic resins as the [C] component. An epoxy resin other than the thermosetting resin having the ability to dissolve the thermoplastic resin and/or a reactive diluent having an epoxy group, and [A], [B],
The ratio of each component in [C] is 1 to 96% by weight,
A resin composition characterized in that the content is 2 to 50% by weight and 2 to 49% by weight. 2. The resin according to claim 1, wherein the epoxy resin having thermoplastic resin dissolving ability as component [C] is a glycidyl ester type epoxy resin and a glycidyl amine type epoxy resin with a viscosity of 150 poise or less (temperature 25 ° C.) Composition. 3 [C] The reactive diluent having an epoxy group as a diepoxy compound includes diglycidyl ether, butanediol diglycidyl ether,
2-glycidyl phenyl glycidyl ether, resorcinol diglycidyl ether, and as monoepoxy compounds, alkylphenol glycidyl ether, phenyl glycidyl ether,
The resin composition according to claim 1, which is butyl glycidyl ether or cresol glycidyl ether. 4. The resin composition according to claim 1, wherein the weight ratio of component [B]/component [C] is 2 or less. 5 [C] The epoxy resin capable of dissolving a thermoplastic resin and/or the reactive diluent having an epoxy group are diglycidyl aniline, diglycidyl toluidine, diglycidyl ether, phenyl glycidyl ether, and cresol glycidyl ether. A resin composition according to claim 1. 6 After dissolving the [B] component in the [C] component, [A]
A resin composition according to claim 1 prepared by mixing the components. The resin composition according to claim 1, which is a glycidyl ester type epoxy resin and a glycidyl amine type epoxy resin. 7. The resin composition according to claim 1, which contains diaminodiphenyl sulfone, dicyandiamide, and BF 3 /monoethylamine as a curing agent for the epoxy resin as component [A].
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23296486A JPS6386758A (en) | 1986-09-30 | 1986-09-30 | Resin composition |
| EP87308550A EP0262891B1 (en) | 1986-09-30 | 1987-09-28 | Resin composition of thermosetting resin and thermoplastic resin |
| DE3751984T DE3751984T2 (en) | 1986-09-30 | 1987-09-28 | Resin composition based on thermosetting resins and thermoplastic resins |
| US07/102,968 US4962162A (en) | 1986-09-30 | 1987-09-30 | Resin composition of thermosetting resin and thermoplastic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23296486A JPS6386758A (en) | 1986-09-30 | 1986-09-30 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6386758A JPS6386758A (en) | 1988-04-18 |
| JPH0580945B2 true JPH0580945B2 (en) | 1993-11-10 |
Family
ID=16947631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23296486A Granted JPS6386758A (en) | 1986-09-30 | 1986-09-30 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6386758A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11387087B2 (en) | 2017-12-15 | 2022-07-12 | Metabolon, Inc. | Method for analyzing small molecule components of a complex mixture, and associated apparatus and computer program product |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311349B1 (en) * | 1987-10-05 | 1996-09-11 | Imperial Chemical Industries Plc | Polymer composition |
| EP3315530B1 (en) | 2015-06-25 | 2022-12-21 | Toray Industries, Inc. | Epoxy resin composition, fiber-reinforced composite material, molded article, and pressure vessel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55137155A (en) * | 1979-03-30 | 1980-10-25 | Toray Ind Inc | Polyester resin composition for molding use |
| JPS5767618A (en) * | 1980-10-15 | 1982-04-24 | Matsushita Electric Works Ltd | Unsaturated polyester refin composition |
| JPS61278555A (en) * | 1985-06-05 | 1986-12-09 | Mitsui Petrochem Ind Ltd | Thermosetting resin composition |
| JPS6222822A (en) * | 1985-07-23 | 1987-01-31 | Toshiba Chem Corp | Sealing resin composition |
| JPS62112622A (en) * | 1985-11-11 | 1987-05-23 | Toshiba Chem Corp | Sealing resin composition |
| JPS62185720A (en) * | 1986-02-12 | 1987-08-14 | Toray Ind Inc | Production of resin composition for prepreg |
-
1986
- 1986-09-30 JP JP23296486A patent/JPS6386758A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55137155A (en) * | 1979-03-30 | 1980-10-25 | Toray Ind Inc | Polyester resin composition for molding use |
| JPS5767618A (en) * | 1980-10-15 | 1982-04-24 | Matsushita Electric Works Ltd | Unsaturated polyester refin composition |
| JPS61278555A (en) * | 1985-06-05 | 1986-12-09 | Mitsui Petrochem Ind Ltd | Thermosetting resin composition |
| JPS6222822A (en) * | 1985-07-23 | 1987-01-31 | Toshiba Chem Corp | Sealing resin composition |
| JPS62112622A (en) * | 1985-11-11 | 1987-05-23 | Toshiba Chem Corp | Sealing resin composition |
| JPS62185720A (en) * | 1986-02-12 | 1987-08-14 | Toray Ind Inc | Production of resin composition for prepreg |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11387087B2 (en) | 2017-12-15 | 2022-07-12 | Metabolon, Inc. | Method for analyzing small molecule components of a complex mixture, and associated apparatus and computer program product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6386758A (en) | 1988-04-18 |
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