JPS6386758A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPS6386758A JPS6386758A JP23296486A JP23296486A JPS6386758A JP S6386758 A JPS6386758 A JP S6386758A JP 23296486 A JP23296486 A JP 23296486A JP 23296486 A JP23296486 A JP 23296486A JP S6386758 A JPS6386758 A JP S6386758A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- component
- resin composition
- epoxy
- glycidyl ether
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 7
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 7
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 7
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 6
- 239000004417 polycarbonate Substances 0.000 claims abstract description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 glycidyl ester Chemical class 0.000 claims abstract description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 5
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 4
- 239000005011 phenolic resin Substances 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 4
- 229920001721 polyimide Polymers 0.000 claims abstract description 4
- 239000009719 polyimide resin Substances 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims abstract description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 9
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229930003836 cresol Natural products 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- OQILSTRGJVCFAG-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound CCCC(O)OCC1CO1 OQILSTRGJVCFAG-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
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004992 toluidines Chemical class 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 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001568 phenolic resin Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 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 7
- 229920001971 elastomer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 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
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 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
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000011134 resol-type phenolic resin 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
- 239000000126 substance Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（技術分野）
本発明は、熱硬化性樹脂と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。Detailed Description of the Invention (Technical Field) The present invention uniformly contains a thermosetting resin and a thermoplastic resin, and combines the excellent mechanical properties and thermal properties of the thermosetting resin with the excellent mechanical properties and thermal properties of the thermoplastic resin. The present invention relates to a resin composition that provides a molded product with good toughness.
〔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
トリッ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
、広く一般産桑、電気分野等に利用されてきた。[Prior art and problems] In recent years, thermosetting resin molded products and composite materials using 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 mulberry production, electrical fields, etc.
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。On the other hand, thermosetting resin molded products have low resin elongation,
It has been pointed out that because of its brittleness, it has poor toughness and impact resistance, and improvements have been sought.
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。Methods for improving the toughness and impact resistance of thermosetting resin molded products 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.
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、用途によっては低配合聞に留まり、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った。ま
た、溶剤を用いて混合させるときは、混合後の脱溶剤に
問題があったり、その１ｉｓＪ法が面倒であったり、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。However, in the case of a method of mixing a rubber component with a thermosetting resin, the toughness and impact resistance of the molded product are improved, but
Since heat resistance and mechanical properties deteriorate, the amount added is regulated, and depending on the application, the amount remains at a low amount, 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 loaded in a vacuum, the composition tended to be non-uniform and the mechanical properties deteriorated. In addition, when mixing using a solvent, there are problems in removing the solvent after mixing, the 1isJ method is troublesome, and a small amount of residual solvent reduces heat resistance.
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。The object of the present invention is to overcome the above-mentioned problems, to be able to uniformly and easily prepare a mixture of thermosetting resin/thermoplastic resin without using a solvent, and to have excellent heat resistance, toughness, and impact strength. It is an object of the present invention to provide a resin composition that provides molded articles with mechanical properties such as the following.
本発明は、（Ａ）成分として熱硬化性樹脂と（Ｂ）成分
として熱可塑性樹脂と（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）の各成分がそれぞれ、１〜９
６ｆｆｌ聞％、２〜５０重盟％、２〜４９重爵％である
ことを特徴とする樹脂組成物である。The present invention comprises a thermosetting resin as the component (A), a thermoplastic resin as the component (B), and an epoxy resin other than the thermosetting resin having the ability to dissolve the thermoplastic resin as the component (C) and/or an epoxy group. , and each component (A), (B), and (C) is 1 to 9
The resin composition is characterized in that the content is 6ffl%, 2 to 50%, and 2 to 49%.
本発明の樹脂組成物では、（Ｃ）成分が、ＣＢ）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。従って、それからｉｑ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、靭性及びそれに伴なう耐衝撃性が著しく改
善されている。In the resin composition of the present invention, the component (C) dissolves the component CB), and the component (C) acts as a mediator between the components (A) and (B), so the preparation method is easy and solvent-free. A uniform mixture of thermosetting resin component/thermoplastic resin component can be obtained by using the following method. Therefore, the molded product obtained from the thermosetting resin component has significantly improved toughness and accompanying impact resistance while retaining the excellent mechanical properties and heat resistance of the thermosetting resin component.
本発明において（Ａ）成分は、エポキシ樹脂、フェノー
ル樹脂、ビスマレイミド樹脂、ポリイミド樹脂等である
。エポキシ樹脂には、ビスフェノールＡ型エポキシ樹脂
（例えば、シェル化学社製エピコート８２８） 、フェ
ノール・ノボラック型エポキシ樹脂（例えば、チバ・ガ
イギー社ＭＥＰＮ１１３８）、クレゾール・ノボラック
型エポキシ樹脂（例えば、日本化桑（株）社製Ｅ○ＣＮ
１０２） 、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ＭＹ ７２０）
があり、これらを単独又は２種以上組合せて使用する。In the present invention, component (A) is an epoxy resin, a phenol resin, a bismaleimide resin, a polyimide resin, or the like. Examples of epoxy resins include bisphenol A type epoxy resins (e.g., Epikote 828 manufactured by Shell Chemical Co., Ltd.), phenol-novolak type epoxy resins (e.g., Ciba Geigy MEPN1138), and cresol-novolac type epoxy resins (e.g., Nippon Kaya Mulberry). E○CN manufactured by Co., Ltd.
102) Glycidylamine type epoxy resin (for example, Araldite MY 720 manufactured by Ciba Geigy)
These can be used alone or in combination.
フェノール樹脂としては、レゾール型フェノール樹脂（
例えば、昭和ユニオン合成（株）社製Ｂ Ｌ Ｓ Ｄ
−３１３５） 、ノボラック型フェノール樹脂（例えば
、三井東圧（株）社製Ｘ Ｌ −２１０Ａ ）がある。As phenolic resin, resol type phenolic resin (
For example, BLSD manufactured by Showa Union Gosei Co., Ltd.
-3135) and novolac type phenolic resins (for example, XL-210A manufactured by Mitsui Toatsu Co., Ltd.).
ビスマレイミド樹脂としては、三菱瓦斯化学（株）社製
ＢＴレジン、ブーツ・テクノヘミ−社製コンビマイト等
がある。ポリイミド樹脂として、ＮＡＳＡで開発された
ＰＭＲ−Ｉｓ、ＬＡＲＣ−１６０１デュポン社製Ｎ Ｒ
−１５０等がある。Examples of the bismaleimide resin include BT resin manufactured by Mitsubishi Gas Chemical Co., Ltd. and Combimite manufactured by Boots Technochemy. As a polyimide resin, PMR-Is developed by NASA, LARC-1601 N R manufactured by DuPont
-150 etc.
熱硬化性樹脂成分として、用途に応じてエポキシ樹脂／
ビスマレイミド樹脂というように、２１以上組合せて使
用することもできる。As a thermosetting resin component, epoxy resin/
It is also possible to use a combination of 21 or more, such as bismaleimide resin.
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、ポリエーテルケトン、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、芳香族ポ
リエステル等があり、これらのうち特にポリカーボネー
ト、ポリスルホン、ポリエーテルスルボン、ポリエーテ
ルイミド、芳香族ポリエステルが均一混合性の面から好
ましい。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。In the present invention, the thermoplastic resin of component (B) includes polycarbonate, polyetherketone, polysulfone,
Examples include polyethersulfone, polyetherimide, aromatic polyester, etc. Among these, polycarbonate, polysulfone, polyethersulfone, polyetherimide, and aromatic polyester are particularly preferred from the viewpoint of homogeneous mixability. Two or more of these thermoplastic resins can also be used in combination.
これらの熱可塑性樹脂（Ｂ）成分は、粒子径４００μ霧
以下、特に１００μ暑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位温度が１００℃以上
のものが好ましい。These thermoplastic resin (B) components are preferably in powder form with a particle size 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.
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、シェル化学社製エピコート １９
１） 、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）等であり、これら
のエポキシ樹脂はＣＢ）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。In the present invention, among component (C), the epoxy resin having thermoplastic resin dissolving ability is a glycidyl ester type epoxy resin (for example, Epicoat 19 manufactured by Shell Chemical Co., Ltd.).
1), glycidylamine type epoxy resins (for example, GOT, GAN manufactured by Nippon Kayaku Co., Ltd.), etc., and these epoxy resins are epoxy resins other than the epoxy resin blended as the CB) component.
（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、ジェポキシ化合物としては、ジグリシジルエー
テル、ブタンジオールグリシジルエーテル１．２−グリ
シジルフェニー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、アルキルフェノールグリシジルエーテル、フェ
ニー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、スチレンオキサイド
等がある。Among the reactive diluents capable of dissolving thermoplastic resins as component (C), examples of jepoxy compounds include diglycidyl ether, butanediol glycidyl ether 1,2-glycidylphenyl glycidyl ether, and resorcinol diglycidyl ether. Examples of the epoxy compound include alkylphenol glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, cresol glycidyl ether, and styrene oxide.
これら（Ｃ）成分は２ｆ１以上組合せて使用することも
できる。また、２５℃の粘度が１５０ボイズ以下のもの
を用いることが好ましい。These (C) components can also be used in combination of 2f1 or more. Further, it is preferable to use a material having a viscosity of 150 voids or less at 25°C.
（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。The combination of component (B) and component (C) is such that component (C) is (
B) It is necessary to have a relationship that dissolves the components, and if this relationship does not exist, the resin composition will not be uniform,
The purpose of the present invention cannot be achieved.
（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。Combinations of component (B) and component (C) that are compatible are as follows.
第 １ 表
ＰＥＳ ：ポリエーテルスルホン
ＰＥＩ（ウルテム）：ポリエーテルイミドＰＳｕ ：ポ
リスルホン
ＰＣ（パンライト）：ポリカーボネートＧＡＮニゲリシ
ジルアニリン
ＧＯＴ ニゲリシジルトルイジン
ＰＧＥ ：フェニルグリシジルエーテルＢＧＥ ニブチ
ルグリシジルエーテル
エビコート１９１ニゲリシジルエステル型エポキシ樹脂
（シェル化学社製）
（Ａ）成分／（Ｂ）成分／〔Ｃ〕酸成分組合せにおいて
、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。Table 1 PES: Polyether sulfone PEI (Ultem): Polyetherimide PSu: Polysulfone PC (Panlite): Polycarbonate GAN Nigericidyl aniline GOT Nigericidyl toluidine PGE: Phenyl glycidyl ether BGE Nibutyl glycidyl ether Ebicoat 191 Ni Gelicidyl ester type epoxy resin (manufactured by Shell Chemical Co., Ltd.) In the (A) component/(B) component/[C] acid component combination, in order to simplify the preparation method, the (B) component was added to the (C) component in advance.
It is preferable to adopt a method of dissolving it in a component and then adding the component (A).
（Ａ）成分／〔Ｂ〕成分／〔Ｃ〕酸成分配合比は、（Ａ
）、ＣＢ）、（Ｃ）がそれぞれ、１〜９６重但％、２〜
５０迅伊％、２〜４９３１１％である。The blending ratio of (A) component/[B] component/[C] acid component is (A
), CB), and (C) are 1 to 96% and 2 to 96%, respectively.
50%, 2-49311%.
（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。ＣＢ）成分の配合量が５０ｒｆＩ邑％より多
いと溶融粘度が高くなり、このため混合、１１間への含
浸や成形がＶＡ＊となり、良好な成形物が得られ難い。If component (A) is outside the predetermined range, the object of the present invention will not be achieved. If the blending amount of component CB) is more than 50rfI%, the melt viscosity will be high, and as a result, mixing, impregnation and molding will result in VA*, making it difficult to obtain a good molded product.
（Ｃ）成分の配合量が４９重黴％より多いと、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
ｆｌｌｆｉ％より少いと本発明の目的は達成されない。If the blending amount of component (C) is more than 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. (B) component and (C) component are each 2
If it is less than fllfi%, the object of the present invention will not be achieved.
ＣＢ）成分／（Ｃ）成分のｆｆ１ｆｆｉ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ａ！帷間への含浸性
が低下しタックも低くなり好ましくない。また、機械的
特性の低下を１ａ来する。（Ｃ）成分の配合ｍ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。The ff1ffi ratio of component (CB)/component (C) is preferably 2 or less. If the ratio exceeds 2, the viscosity of the composition will increase, making it difficult to handle, and when used as a prepreg, a! This is undesirable because it impregnates the fabric and the tack becomes low. In addition, mechanical properties are reduced by 1a. (C) The composition m of the component is (B)
In relation to the blending amounts of the components, it is preferable to keep the amount to a minimum so that the resin composition has a uniform composition.
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、使用条件によって、強化材料、例え
ばガラス繊組、炭素繊組、芳香族ポリアミド繊維、金ｙ
Ａ繊維等を加えることもできる。また、ブタジェン−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、を色材等
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。In addition to the above-mentioned essential components, the resin composition of the present invention may also include reinforcing materials such as glass fibers, carbon fibers, aromatic polyamide fibers, gold, etc. depending on the purpose, application, and conditions of use.
A fiber etc. can also be added. Furthermore, polymeric reinforcing materials such as butadiene-acrylonitrile rubber, flame retardants such as antimony trioxide, fillers such as silica powder, coloring materials, etc. can also be added. Depending on the type of resin used, some may or may not require initiators, curing agents, and curing accelerators for the crosslinking reaction, and these may be selected as appropriate according to the needs of the resin composition of the present invention. can be prepared, for example, by the following method.
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。That is, each component is supplied to a kneading device and heated and kneaded, preferably under an inert gas atmosphere. The heating temperature at this time is lower than the curing start temperature of the thermosetting resin.
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。Alternatively, after dissolving component (C) in component (B), (A)
Add the ingredients and, if necessary, a curing agent, etc., and knead.
通常は２０〜２００℃の温度、特に好ましくは５０〜１
５０℃の温度にて調製する。Usually at a temperature of 20 to 200°C, particularly preferably 50 to 1
Prepare at a temperature of 50°C.
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、所謂ホットメルト法
により行うことができる。When preparing a prepreg by impregnating reinforcing fibers with the resin composition of the present invention, the so-called hot melt method, which is already known, can be used.
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（＊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。Further, methods for molding the resin composition of the present invention include heat curing, UV (*external beam) curing, EB (electron beam) curing, and moisture curing, but the combination of methods and curing means is thermal curing. It can be selected depending on the type of resin.
本発明の樹脂組成物は、（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ろう
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）成分が成
る大ぎさの相となって析出してくる場合もあるが、その
場合でも単純に（Ａ〕酸成分（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
。The resin composition of the present invention comprises a thermosetting resin as component (A) and (
Since the component (C) is present as a mediator for the thermoplastic resin of the component B), a resin composition in which each component is uniformly mixed is obtained, and there is no influence of residual solvent, and the thermosetting resin has excellent heat resistance. It would be an excellent resin composition that has both the toughness and impact strength of a thermoplastic resin.Also, due to solubility issues, a homogeneous mixture of components (B) and (C) was mixed with component (A). In some cases, the (B) component may precipitate as a large phase, but even in that case, the mixed state will be more uniform than when the (A) acid component (B) component is simply mixed. It goes without saying that there is.
このものは、単独成形物にて或いはｍ維強化材との複合
材料成形物にて１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。This product can be used in a wide range of fields such as the 1-ki field, the medical field, the aerospace field, the civil engineering/architecture field, and the general industrial field, either as a single molded product or as a composite molded product with m-fiber reinforcement.
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。Hereinafter, the present invention will be explained with reference to examples, and comparative examples will be shown.
実施例１〜５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
よう計耐してビーカーに取った。これを、１１０℃、１
時間ｉ＋ｙしながら加熱させ、均一な（Ａ）、（８）、
（Ｃ）成分の混合物を１ｑた。Examples 1 to 5 and Comparative Examples 1 to 7 Using an epoxy resin as the (A) component, (A), [B]
, and (C) were placed in a beaker so that the types and blending ratios shown in Table 2 were maintained. This was heated to 110℃ for 1
Heating for time i + y, uniform (A), (8),
1 q of the mixture of component (C) was obtained.
さらに、ジアミノジフェ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１！７だ。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１ワた。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 of 1:7. This composition was placed in a silicone rubber mold and cured under pressure at 180° C. for 2 hours to give a cured product of the resin composition.
硬化物より試験片をのり出し、ガラス転移温度の測定、
１ｄ１８靭性試験及びアイゾツト衝撃試験を行った。得
られた結果をまとめて第２表に示す。Extrude a test piece from the cured product and measure the glass transition temperature.
A 1d18 toughness test and an Izod impact test were conducted. The obtained results are summarized in Table 2.
また、比較例として、（Ａ）成分のみの系（比較例１〜
５）、ＣＢ）成分を入れない系（比較例６）、及び（Ｂ
）成分の代りに宇部興産（株）社製ブタジェン−アクリ
ロニトリルゴムＣＴ Ｂ Ｎ 、 ＨＹｃａｒ１３００
ｘ 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。In addition, as a comparative example, a system containing only the component (A) (Comparative Examples 1 to
5), CB) system without component (Comparative Example 6), and (B
) butadiene-acrylonitrile rubber CTBN, HYcar1300 manufactured by Ube Industries, Ltd.
Regarding the system containing x 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.
以上の結果によれば、実施例１〜５の場合は、比較例に
比べ、破壊靭性及びアイゾツト衝撃強さに侵れ、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、耐熱性の低実施例６〜１０及び比較例８〜１２
（Ａ）成分にフェノール樹脂又はビスマレイミド樹脂を
用い、他は実施例１〜５と同様な操作により硬化物を得
た。硬化物について物性をこの結果によれば、実施例の
場合は、比較例に比べ、破壊靭性、アイゾツト衝撃強さ
に優れることがわかる。According to the above results, it can be seen that Examples 1 to 5 have better fracture toughness and Izot impact strength than Comparative Examples, and are rich in toughness. In addition, in the case of Comparative Example 7, the toughness is excellent, but the heat resistance is low. A cured product was obtained by the same operation as above. According to the results of the physical properties of the cured products, it can be seen that the Examples are superior in fracture toughness and Izot impact strength compared to the Comparative Examples.
Claims (8)
して熱可塑性樹脂と、（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。(1) A thermosetting resin as the (A) component, a thermoplastic resin as the (B) component, and an epoxy resin other than the thermosetting resin and/or epoxy that has the ability to dissolve the thermoplastic resin as the (C) component. and a reactive diluent having a group, and the ratio of each component (A), (B), and (C) is 1 to 1, respectively.
A resin composition characterized in that the content is 96% by weight, 2 to 50% by weight, and 2 to 49% by weight.
ェノール樹脂、ビスマレイミド樹脂、ポリイミド樹脂で
ある特許請求の範囲（１）項記載の樹脂組成物。(2) The resin composition according to claim (1), wherein the thermosetting resin of component [A] is an epoxy resin, a phenol resin, a bismaleimide resin, or a polyimide resin.
、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、芳香族ポリエステルである特許請求の範囲（１
）項記載の樹脂組成物。(3) Claims (1) in which the thermoplastic resin of component [B] is polycarbonate, polysulfone, polyethersulfone, polyetherimide, or aromatic polyester.
) The resin composition described in item 1.
シ樹脂が、粘度１５０ポイズ（温度２５℃）以下のグリ
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
組成物。(4) Claim (1) wherein the epoxy resin capable of dissolving thermoplastic resin as component [C] is a glycidyl ester type epoxy resin or a glycidyl amine type epoxy resin with a viscosity of 150 poise or less (temperature 25°C). The resin composition described.
、ジエポキシ化合物として、ジグリシジルエーテル、ブ
タンジオールグリシジルエーテル、２−グリシジルフェ
ニー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
ルフェノールグリシジルエーテル、フェニールグリシジ
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、スチレンオキサイドである特許請求
の範囲（１）項記載の樹脂組成物。(5) The reactive diluent having an epoxy group as the [C] component is diglycidyl ether, butanediol glycidyl ether, 2-glycidyl phenyl glycidyl ether, resorcinol diglycidyl ether as a diepoxy compound, and as a monoepoxy compound, The resin composition according to claim (1), which is alkylphenol glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, cresol glycidyl ether, or styrene oxide.
る特許請求の範囲（１）項記載の樹脂組成物。(6) The resin composition according to claim (1), wherein the weight ratio of component [B]/component [C] is 2 or less.
リエーテルスルホン、ポリエーテルイミドであり、〔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、フェニー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。(7) [B] component thermoplastic resin is polysulfone, polyethersulfone, polyetherimide, [C
] Claims in which the epoxy resin capable of dissolving 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. The resin composition described in (1).
分と混合することによって調製された特許請求の範囲（
１）項記載の樹脂組成物。(8) Claims prepared by dissolving component [B] in component [C] and then mixing with component [A] (
1) The resin composition described in item 1).
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 true JPS6386758A (en) | 1988-04-18 |
| JPH0580945B2 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0258569A (en) * | 1987-10-05 | 1990-02-27 | Imperial Chem Ind Plc <Ici> | Polymer composition |
| WO2016208618A1 (en) | 2015-06-25 | 2016-12-29 | 東レ株式会社 | Epoxy resin composition, fiber-reinforced composite material, molded article, and pressure vessel |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019116288A1 (en) | 2017-12-15 | 2019-06-20 | Metabolon, Inc. | Method for analyzing small molecule components of a complex mixture, and associated apparatus and computer program product |
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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0258569A (en) * | 1987-10-05 | 1990-02-27 | Imperial Chem Ind Plc <Ici> | Polymer composition |
| WO2016208618A1 (en) | 2015-06-25 | 2016-12-29 | 東レ株式会社 | Epoxy resin composition, fiber-reinforced composite material, molded article, and pressure vessel |
| KR20180022778A (en) | 2015-06-25 | 2018-03-06 | 도레이 카부시키가이샤 | Epoxy resin composition, fiber reinforced composite material, molded article and pressure vessel |
| US10696805B2 (en) | 2015-06-25 | 2020-06-30 | Toray Industries, Inc. | Epoxy resin composition, fiber reinforced composite material, molded article, and pressure vessel |
| US11186691B2 (en) | 2015-06-25 | 2021-11-30 | Toray Industries, Inc. | Epoxy resin composition, fiber reinforced composite material, molded article and pressure vessel |
| US11186692B2 (en) | 2015-06-25 | 2021-11-30 | Toray Industries, Inc. | Epoxy resin composition, fiber reinforced composite material, molded article and pressure vessel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0580945B2 (en) | 1993-11-10 |
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