JPH02103223A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH02103223A JPH02103223A JP25817488A JP25817488A JPH02103223A JP H02103223 A JPH02103223 A JP H02103223A JP 25817488 A JP25817488 A JP 25817488A JP 25817488 A JP25817488 A JP 25817488A JP H02103223 A JPH02103223 A JP H02103223A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- molecular weight
- average molecular
- weight
- number average
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title description 30
- 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 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 7
- -1 aliphatic group hydrocarbon Chemical class 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 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 12
- 239000004593 Epoxy Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000270666 Testudines Species 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000014347 soups Nutrition 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、エポキシ樹脂組成物に関するものであり、更
に詳しくは、弾性率、硬度、耐熱性に優れていると共に
、特に靭性に優れ、例えば土木建築用材料、塗料、ライ
ニング材、接着剤、電気機器成形材料、機械部品、治工
具、繊維強化複合材料(以下FrtPと略す)用のマト
リクス樹脂として有用なエポキシ樹脂組成物に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition, and more specifically, it relates to an epoxy resin composition that is excellent in elastic modulus, hardness, and heat resistance, and particularly has excellent toughness, such as The present invention relates to an epoxy resin composition useful as a matrix resin for civil engineering and construction materials, paints, lining materials, adhesives, electrical equipment molding materials, machine parts, jigs, and fiber reinforced composite materials (hereinafter abbreviated as FrtP).
従来、エポキシ樹脂は、耐熱性、弾性率、硬度および耐
薬品性に優れ、特にアラミド繊維、ガラス繊維及び炭素
繊維などの強化繊維を含有する複合材料用のマトリクス
樹脂として広く用いられているものであるが、その用途
や使用方法によって種々の問題点を有する。たとえばF
RP用マトリクス樹脂として用いた場合、FRPの機械
的強度、とりわけ#撃特性や疲労特性等に影響を与える
靭性が不充分であるといった問題があった。このためエ
ポキシ樹脂をマトリクス樹脂として使用する場合には、
可撓性を付与し、更には機械的強度、特に靭性を向上さ
せるために硬化剤や可撓性付与剤を添加することが行な
われている。Conventionally, epoxy resins have excellent heat resistance, elastic modulus, hardness, and chemical resistance, and are widely used as matrix resins for composite materials, especially those containing reinforcing fibers such as aramid fibers, glass fibers, and carbon fibers. However, there are various problems depending on the purpose and method of use. For example, F
When used as a matrix resin for RP, there is a problem that the mechanical strength of FRP is insufficient, especially the toughness that affects impact properties, fatigue properties, etc. Therefore, when using epoxy resin as a matrix resin,
In order to impart flexibility and further improve mechanical strength, particularly toughness, hardening agents and flexibility imparting agents are added.
しかしながら、このような従来の方法では、エポキシ樹
脂硬化物の可撓性は成る程度改善することはできるが、
エポキシ樹脂硬化物の本来の特徴である弾性率、硬度及
び耐熱性等の物性の著しい低下が見られ、たとえばFR
Pの靭性の大きな改善を図り得ないばかりか、更には耐
薬品性、耐候性。However, with such conventional methods, although the flexibility of the cured epoxy resin product can be improved to some extent,
A significant decrease in physical properties such as elastic modulus, hardness, and heat resistance, which are the original characteristics of cured epoxy resins, was observed, and for example, FR
Not only is it impossible to significantly improve the toughness of P, but also the chemical resistance and weather resistance.
耐水性等をも低下させるといった新たな問題が生じる。A new problem arises in that water resistance and the like are also reduced.
一方、特開昭62−127317号には、−分子中に少
なくとも二個以上のポリエポキシ化合物、高分子量エポ
キシ樹脂、ジシアンジアミド、及び/又は硬化促進剤か
らなるプリプレグ用エポキシ樹脂組成物が開示されてい
る。On the other hand, JP-A-62-127317 discloses an epoxy resin composition for prepregs comprising at least two polyepoxy compounds, a high molecular weight epoxy resin, dicyandiamide, and/or a curing accelerator in the molecule. There is.
しかしながら、このようなエポキシ樹脂組成物をプリプ
レグ用エポキシ樹脂組成物として使用した場合には、タ
ック性、ドレープ性、樹脂フロー性、作業性、保存安定
性等に問題があり、その改善が望まれていた。However, when such epoxy resin compositions are used as prepreg epoxy resin compositions, there are problems with tackiness, drape properties, resin flow properties, workability, storage stability, etc., and improvements are desired. was.
この点を改善するため、本発明者らは先に[ビスフェノ
ールA系エポキシ樹脂とエポキシ樹脂硬化剤とを含有し
、前記ビスフェノールA系エポキシ樹脂は、エポキシ当
量が190以下のものを40重量部以下含み、全体の数
平均分子量は600〜1300であることを特徴とする
エポキシ樹脂組成物」を提案した(特願昭63−773
25号)。In order to improve this point, the present inventors first [contains a bisphenol A-based epoxy resin and an epoxy resin curing agent, and the bisphenol A-based epoxy resin has an epoxy equivalent of 190 or less and 40 parts by weight or less. "an epoxy resin composition characterized by having a total number average molecular weight of 600 to 1,300" (Japanese Patent Application No. 63-773)
No. 25).
かかるエポキシ樹脂組成物はプリプレグ用樹脂として用
いた時のタック性、ドレープ性、作業性及び保存安定性
に優れたものであるが、その後の本発明者らの検討によ
れば、このエポキシ樹脂は数平均分子量が高くその溶融
粘度も高いことから、常温あるいはそれ以下の温度では
タック性やドレープ性が必ずしも良好なものとはいえず
、更には環境温度によってタック性やドレープ性が変化
してしまい、広い温度範囲で安定した性状を示すもので
なく、また靭性や可撓性等の機械的物性に若干の問題点
があることが判明した。This epoxy resin composition has excellent tackiness, drapeability, workability, and storage stability when used as a prepreg resin, but according to subsequent studies by the present inventors, this epoxy resin has Due to its high number average molecular weight and high melt viscosity, it does not necessarily have good tack and drape properties at room temperature or lower temperatures, and furthermore, its tack and drape properties change depending on the environmental temperature. It was found that these materials did not exhibit stable properties over a wide temperature range, and that there were some problems with mechanical properties such as toughness and flexibility.
本発明はかかる事情に鑑みてなされたものであって、そ
の目的は高温下はもとより常温あるいはそれ以下の温度
下においても優れたタック性及びドレープ性を示し、し
かもこれらの性状が広い温度範囲に亘って安定に持続す
ると共に靭性や可撓性等の機械的性能等の優れた成形体
を与えるエポキシ樹脂組成物を提供することにある。The present invention was made in view of the above circumstances, and its purpose is to exhibit excellent tack and drape properties not only at high temperatures but also at room temperature or lower temperatures, and which also exhibits excellent tack and drape properties over a wide temperature range. The object of the present invention is to provide an epoxy resin composition that remains stable over a long period of time and provides a molded article with excellent mechanical properties such as toughness and flexibility.
本発明者らの検討によれば、上記目的は特定範囲の数平
均分子量をもち、かつ特定の分子量分布を有するエポキ
シ樹脂を用いると共に特定のエポキシ樹脂硬化剤を併用
することによって達成できることが知見された。According to the studies of the present inventors, it has been found that the above object can be achieved by using an epoxy resin having a number average molecular weight in a specific range and a specific molecular weight distribution, and by using a specific epoxy resin curing agent. Ta.
すなわち、本発明のエポキシ樹脂組成物はビスフェノー
ルA系エポキシ樹脂とエポキシ樹脂硬化剤とを含有し、
前記ビスフェノールA系エポキシ樹脂は、数平均分子量
が450〜700であり、かつその重量平均分子量と数
平均分子量の比(重量平均分子量/数平均分子量)が1
.3〜3.0であり、前記エポキシ樹脂硬化剤は、下記
−形式
%式%
(式中、R1及びR2はアルキル基、シクロアルキル基
、アリール基又はアラルキル基を、Aは置換基を有して
もよい二価の脂肪族炭化水素基を表わす)
で示されるエポキシ樹脂硬化剤であることを特徴とする
。That is, the epoxy resin composition of the present invention contains a bisphenol A-based epoxy resin and an epoxy resin curing agent,
The bisphenol A-based epoxy resin has a number average molecular weight of 450 to 700, and a ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight) of 1.
.. 3 to 3.0, and the epoxy resin curing agent has the following formula: (representing an optional divalent aliphatic hydrocarbon group).
本発明で用いるビスフェノールA系エポキシ樹脂の第1
の特徴はその数平均分子量が450〜700、好ましく
は500〜650の範囲にあることである。数平均分子
量が450未満であると、低分子量成分が多くなり過ぎ
、得られるプリプレグのタック性やドレープ性が劣り、
また硬化時に樹脂フロー性が大きくなり、更には硬化物
の物性特に靭性が低下し、本発明の所期の目的を達成で
きない。また数平均分子量が700を越えると、靭性を
はじめとする良好な硬化物物性が得られるものの、低分
子量成分が少ないために常温下でのタック性やドレープ
性が低下し、それより低温下ではタック性やドレープ性
の性状が更に悪化し、プリプレグとして取り扱うことが
不可能となる。The first bisphenol A-based epoxy resin used in the present invention
is characterized in that its number average molecular weight is in the range of 450-700, preferably 500-650. If the number average molecular weight is less than 450, the amount of low molecular weight components will be too large, resulting in poor tackiness and drape properties of the resulting prepreg.
Moreover, resin flowability increases during curing, and furthermore, physical properties, particularly toughness, of the cured product deteriorate, making it impossible to achieve the intended purpose of the present invention. In addition, when the number average molecular weight exceeds 700, good physical properties of the cured product including toughness can be obtained, but the tackiness and drape properties at room temperature decrease due to the lack of low molecular weight components, and at lower temperatures. The tackiness and drape properties deteriorate further, making it impossible to handle it as a prepreg.
本発明で用いるエポキシ樹脂の第2の特徴は。The second feature of the epoxy resin used in the present invention is.
重量平均分子量と数平均分子量の比(重量平均分子量/
数平均分子りが1.3〜:3.0、好ましくは1.5〜
2.7の範囲にあることである。Ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/
Number average molecular weight: 1.3~3.0, preferably 1.5~
It is within the range of 2.7.
重量平均分子量と数平均分子量の比(重量平均分子ff
l/数平均分子量)が1.3未満であると、低分子量成
分が多くなり過ぎ、数平均分子量が450未満と同様な
欠点を生じる。また重量平均分子量と数平均分子量の比
(重量平均分子量/数平均分子量)が3.0を越えると
、高分子量成分が多くなり過ぎ、数平均分子量が700
を越えた場合と同様な結果を生じるので好ましくない。Ratio of weight average molecular weight to number average molecular weight (weight average molecular weight ff
When the ratio (l/number average molecular weight) is less than 1.3, the amount of low molecular weight components becomes too large, resulting in the same drawbacks as when the number average molecular weight is less than 450. If the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight) exceeds 3.0, the high molecular weight component will be too large and the number average molecular weight will be 700.
This is not preferable because the same result will occur if the value is exceeded.
本発明で用いるビスフェノールA系エポキシ樹脂は、例
えば、油化シェル■製のエピコート828.10o1.
1004.1007.1009.1010(商品名)等
を適宜混合することによって調製できる。The bisphenol A-based epoxy resin used in the present invention is, for example, Epicoat 828.10o1 manufactured by Yuka Shell ■.
It can be prepared by appropriately mixing 1004.1007.1009.1010 (trade name) and the like.
更に、本発明者らの検討によれば、一般式(1)%式%
(1)
(式中、R,及びR2はアルキル基、シクロアルキル基
、アリール基又はアラルキル基を、Aは置換基を有して
もよい二価の脂肪族炭化水素基を表わす)
で示されるエポキシ樹脂硬化剤を、上記ビスフェノール
A系エポキシ樹脂と共に使用してエポキシ樹脂組成物を
調製した場合には鎖状高分子が容易に形成され、特に靭
性の点で優れたエポキシ樹脂硬化物が得られることが知
見された。Furthermore, according to the studies of the present inventors, general formula (1)% formula%
(1) (wherein R and R2 represent an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and A represents a divalent aliphatic hydrocarbon group which may have a substituent) When an epoxy resin composition is prepared by using an epoxy resin curing agent together with the above-mentioned bisphenol A-based epoxy resin, a chain polymer is easily formed, and a cured epoxy resin product that is particularly excellent in toughness can be obtained. It was discovered that
本発明で用いる前記一般式(1)で示される第2級アミ
ン誘導体の構造式において、R1は低級アルキル基(例
えば炭素数1〜6)であることが好ましい。In the structural formula of the secondary amine derivative represented by the general formula (1) used in the present invention, R1 is preferably a lower alkyl group (for example, having 1 to 6 carbon atoms).
また、全R1及び82950モル1以上、好ましくは8
0モル%以上がアルキル基であることが望ましい。In addition, total R1 and 82950 mol 1 or more, preferably 8
It is desirable that 0 mol% or more is an alkyl group.
又、炭素数1−6といった低級のアルキル基の中でも特
に炭素数1〜3のアルキル基が好ましく、炭素数が7以
上となるとエポキシ樹脂硬化物の硬度、耐熱性が低下す
るという欠点が生じてくる。Furthermore, among lower alkyl groups having 1 to 6 carbon atoms, alkyl groups having 1 to 3 carbon atoms are particularly preferable; if the number of carbon atoms is 7 or more, the hardness and heat resistance of the cured epoxy resin may decrease. come.
また、上記一般式(1)で示される第2級アミン誘導体
において、Aは置換基を有していてもよい二価の脂肪族
炭化水素基であるが、この場合、二価の脂肪族炭化水素
基としては、炭素数1〜5のアルキレン基が、置換基と
しては、アルキル基、アリール基、ハロゲン、水酸基な
どが挙げられる。Further, in the secondary amine derivative represented by the above general formula (1), A is a divalent aliphatic hydrocarbon group which may have a substituent; Examples of hydrogen groups include alkylene groups having 1 to 5 carbon atoms, and examples of substituents include alkyl groups, aryl groups, halogens, and hydroxyl groups.
以下、一般式(1)で示される第2級アミン誘導体の具
体例を例示する。Specific examples of the secondary amine derivative represented by the general formula (1) will be illustrated below.
CH,NH戒(1□足NllCl!。CH, NH Kai (1 □ foot NllCl!.
Cl5NH(CI+□汁補CH。Cl5NH (CI + □ Soup supplementary CH.
C113NH米H2いHCI+。C113NH rice H2 HCI+.
CH,NH<H,3T−NHCH。CH, NH<H, 3T-NHCH.
Cl3NH−(c)1.WLH。Cl3NH-(c)1. W.L.H.
I4H,NH米11吉→HらI5 C1+3 CH,NH−CII−CH□−NIIC2)1゜−・ Cl3NH−CH−CH,−CH2C7H。I4H, NH rice 11-kichi → H et al. I5 C1+3 CH,NH-CII-CH□-NIIC2)1゜-・ Cl3NH-CH-CH, -CH2C7H.
CH3 CH,NH−C−CH2−N)ICH。CH3 CH,NH-C-CH2-N)ICH.
CI(。CI(.
CH3 Cl3NH−C)!2−C−CH,−NHcI+。CH3 Cl3NH-C)! 2-C-CH, -NHcI+.
H CH3N1(−CH−CI2−NIICI+。H CH3N1(-CH-CI2-NIICI+.
r
Cl3NH(−CI(−CI、 −N)IcI(3LI
本発明のアミン系硬化剤は前記したように一般式(I)
で表わされる第2級アミンであるが、必要に応じ後記す
る従来公知の他の硬化剤あるいは反応促進剤を併用する
ことも可能である。rCl3NH(-CI(-CI, -N)IcI(3LI) As described above, the amine curing agent of the present invention has the general formula (I)
Although the secondary amine is represented by, it is also possible to use other conventionally known curing agents or reaction accelerators as described below in combination, if necessary.
本発明に係るエポキシ樹脂プリプレグが機械的物性とく
に靭性や可撓性に優れると共に作業安定性や貯蔵安定性
に優れる理由は現時点で定がでないが次のような事由に
よるものと思われる。The reason why the epoxy resin prepreg according to the present invention has excellent mechanical properties, particularly toughness and flexibility, as well as excellent work stability and storage stability, is not clear at present, but it is thought to be due to the following reasons.
(1)本発明の硬化剤は第2級アミンを主成分としてい
ることから、直鎖の分子鎖を形成する。(1) Since the curing agent of the present invention contains a secondary amine as a main component, it forms a linear molecular chain.
(2)このような直鎖の分子鎖は硬化反応の初期ゲル化
に先立って形成されることがゲルパーミニージョンクロ
マトグラフィー(GPC)を用いた解析で明らかとされ
、従って、この直鎖の分子鎖と高分子量ビスフェノール
A系エポキシ樹脂により硬化物中に鎖状分子成分が多く
なり、靭性が向上する。(2) Analysis using gel permeation chromatography (GPC) has revealed that such linear molecular chains are formed prior to the initial gelation of the curing reaction. The molecular chains and high molecular weight bisphenol A-based epoxy resin increase the chain molecular components in the cured product, improving toughness.
(3)高分子量と低分子量のビスフェノールA系エポキ
シ樹脂が、適度に配合されているために、製造したプリ
プレグが好適な溶融粘度と温度依存性のない安定かつ好
適なタック性、ドレープ性を示す。(3) Because high molecular weight and low molecular weight bisphenol A-based epoxy resins are appropriately blended, the manufactured prepreg exhibits suitable melt viscosity and stable and suitable tackiness and drape properties without temperature dependence. .
本発明で用いるエポキシ樹脂硬化剤は、上記ビスフェノ
ールA系エポキシ樹脂の1当量に対し通常活性水素当量
で0.6〜1.4、好ましくは0.8〜1.2の割合で
配合される。硬化剤の活性水素当量比が0.6未満又は
1.4より大きい場合には、エポキシ樹脂硬化剤の耐熱
性、硬度が低下することとなり好ましくない。The epoxy resin curing agent used in the present invention is usually blended in an active hydrogen equivalent ratio of 0.6 to 1.4, preferably 0.8 to 1.2, per equivalent of the bisphenol A-based epoxy resin. If the active hydrogen equivalent ratio of the curing agent is less than 0.6 or greater than 1.4, the heat resistance and hardness of the epoxy resin curing agent will decrease, which is not preferable.
本発明によると上記硬化剤は、そのまま或いは溶剤に溶
解して、常温又は例えば50℃に加温してビスフェノー
ルA系エポキシ樹脂と混合すればよい。溶剤としては、
ケトン類(アセトン、メチルエチルケトン、メチルイソ
ブチルケトン等)、セロソルブ類(メチルセルソルブ、
エチルセルソルブ等)、アミド類(ジメチルホルムアミ
ド等)が好ましい、又、本発明に係るエポキシ樹脂組成
物の硬化条件は通常130℃で2時間、好ましくは13
0℃で2時間硬化をさせた後、180℃で2時間の後硬
化を施したものである。According to the present invention, the curing agent may be mixed with the bisphenol A-based epoxy resin either as it is or dissolved in a solvent, heated to room temperature or, for example, 50°C. As a solvent,
Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (methyl cellosolve,
Ethyl cellosolve, etc.), amides (dimethylformamide, etc.) are preferred, and the curing conditions for the epoxy resin composition according to the present invention are usually 130°C for 2 hours, preferably 130°C.
After curing at 0°C for 2 hours, post-curing was performed at 180°C for 2 hours.
更に、本発明のエポキシ樹脂組成物を調製するに際して
は、必要に応じて、オレフィンオキサイド、グリシジル
メタクリレート、スチレンオキサイド、フェニルグリシ
ジルエーテル等の反応性稀釈剤;フェノール類、3級ア
ミン類、イミダゾール類、三弗化ホウ素の錯塩、ピラゾ
ール類、アミノトリアゾール等の硬化促進剤;更にはシ
リカ粉末、アルミニウム粉末、マイカ、炭素カルシウム
等の充填剤を加えることもできる。通常これらの添加物
の使用量は、硬化剤とエポキシ樹脂の配合物に対し1反
応性稀釈剤は0〜15重量%、硬化促進剤は0〜5重量
%、充填剤は0〜70重景%とされる。Furthermore, when preparing the epoxy resin composition of the present invention, reactive diluents such as olefin oxide, glycidyl methacrylate, styrene oxide, and phenyl glycidyl ether; phenols, tertiary amines, imidazoles, Hardening accelerators such as complex salts of boron trifluoride, pyrazoles, and aminotriazole; and fillers such as silica powder, aluminum powder, mica, and calcium carbonate may also be added. Usually, the amount of these additives used is 0 to 15% by weight for a reactive diluent, 0 to 5% by weight for a curing accelerator, and 0 to 70% by weight for a filler, based on the mixture of hardener and epoxy resin. %.
本発明の他の態様によれば、特に多少靭性を犠牲にして
も耐熱性等を向上させたい場合には、更に、エポキシ樹
脂成分としてビスフェノールA系エポキシ樹脂とは異な
る他のエポキシ樹脂を全エポキシ樹脂100重量部に対
して50重量部以下含有させることができる。この場合
能のエポキシ樹脂の含有量が50重量部を越えると靭性
を著しく低下させることとなり好ましくない。According to another aspect of the present invention, when it is desired to improve heat resistance etc. even at the cost of some toughness, another epoxy resin other than the bisphenol A-based epoxy resin may be added as an epoxy resin component to the whole epoxy resin. It can be contained in an amount of 50 parts by weight or less per 100 parts by weight of the resin. In this case, if the content of the functional epoxy resin exceeds 50 parts by weight, the toughness will be significantly reduced, which is not preferable.
他のエポキシ樹脂としては、任意の通常市販されている
エポキシ樹脂を一種又は複数種選択して使用し得るが、
例えば、グリシジルエーテル系エポキシ樹脂(ビスフェ
ノールA、F、S系エポキシ樹脂、ノボラック系エポキ
シ樹脂、臭素化ビスフェノールA系エポキシ樹脂)、環
式脂肪族エポキシ樹脂、グリシジルエステル系エポキシ
樹脂、グリシジルアミン系エポキシ樹脂、複素環式エポ
キシ樹脂を挙げることができる。As the other epoxy resin, one or more kinds of epoxy resins that are commonly available on the market can be selected and used.
For example, glycidyl ether-based epoxy resins (bisphenol A, F, S-based epoxy resins, novolac-based epoxy resins, brominated bisphenol A-based epoxy resins), cycloaliphatic epoxy resins, glycidyl ester-based epoxy resins, glycidyl amine-based epoxy resins. , heterocyclic epoxy resins.
以下、実施例及び比較例により本発明を更に詳細に説明
する。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例1〜6
本実施例では、ビスフェノールA系エポキシ樹脂として
、エピコート828(エポキシ当量184〜194、数
平均分子量380)、1001(エポキシ当量450〜
500、数平均分子量900)、1004(エポキシ当
量875〜975、数平均分子量1600)、1007
(エポキシ当量1750〜2200、数平均分子量2
900)、1009(エポキシ当量2400〜3300
、数平均分子量3750)及び1010(エポキシ当量
3000−sooo 、数平均分子量5500) (油
化シェル■製、商品名)を、硬化剤としては表−1に示
される化合物を使用し、表−1に示す割合でvR製しプ
リプレグ用のマトリクス樹脂を調製した。Examples 1 to 6 In this example, as bisphenol A-based epoxy resins, Epicote 828 (epoxy equivalent weight 184 to 194, number average molecular weight 380), 1001 (epoxy equivalent weight 450 to
500, number average molecular weight 900), 1004 (epoxy equivalent weight 875-975, number average molecular weight 1600), 1007
(Epoxy equivalent weight 1750-2200, number average molecular weight 2
900), 1009 (epoxy equivalent 2400-3300
, number average molecular weight 3750) and 1010 (epoxy equivalent weight 3000-sooo, number average molecular weight 5500) (manufactured by Yuka Shell ■, trade name), and the compounds shown in Table 1 as curing agents were used. A matrix resin for prepreg was prepared by vR in the proportions shown below.
尚、実施例6では、ビスフェノールA系エポキシ樹脂と
は異なるエポキシ樹脂成分の一例として更にエピコート
152(エポキシ当量172〜179、数平均分子量3
70) (油化シェル■製、商品名)を20重量部添加
した。In Example 6, Epikote 152 (epoxy equivalent: 172 to 179, number average molecular weight: 3
70) (manufactured by Yuka Shell ■, trade name) was added in an amount of 20 parts by weight.
各実施例において、表−1に示すエポキシ樹脂成分を1
50℃で加熱混合した。この混合物を80℃まで冷却し
、表−1に示す配合比で調製されたエポキシ樹脂硬化剤
を化学量論量添加して、常温で高靭性を有するエポキシ
樹脂組成物を調製した。In each example, 1 epoxy resin component shown in Table 1 was added.
The mixture was heated and mixed at 50°C. This mixture was cooled to 80° C., and a stoichiometric amount of an epoxy resin curing agent prepared at the compounding ratio shown in Table 1 was added to prepare an epoxy resin composition having high toughness at room temperature.
これを2枚のガラス板とテフロンのスペーサから成る型
に流し込み、100℃、2時間加熱し、更に200℃、
2時間オーブン中で加熱し、硬化させた。This was poured into a mold consisting of two glass plates and a Teflon spacer, heated at 100°C for 2 hours, then further heated to 200°C.
It was heated in an oven for 2 hours to cure.
このようにして得られたエポキシ樹脂硬化物は30cm
X 30cm X 3mmの樹脂注型板から試験片を
切り出し、アイゾツト衝撃強度(IZOD)を測定した
。その結果を表−1に示す。このものは耐熱性を有し、
特に靭性の優れたエポキシ樹脂であった。The epoxy resin cured product thus obtained is 30 cm
A test piece was cut out from a resin casting plate measuring 30 cm x 3 mm, and its Izod impact strength (IZOD) was measured. The results are shown in Table-1. This material has heat resistance,
It was an epoxy resin with particularly excellent toughness.
また、上記で得たエポキシ樹脂を一方向に揃えた炭素繊
維(強度350kg10I!1.弾性率32t/mm2
)に含浸させ、プリプレグを得た。このプリプレグはタ
ック性に優れ、また15〜30℃の温度範囲においても
タック性が変化せず、タック性の温度依存性がないこと
が分った。これを12N積層し、上述の硬化条件で加熱
して成形体を得た。この成形体の衝撃後圧縮強度(CA
I)を測定した結果を表−1に示す。In addition, carbon fibers with the epoxy resin obtained above aligned in one direction (strength 350 kg 10 I! 1, elastic modulus 32 t/mm2
) to obtain prepreg. It was found that this prepreg had excellent tackiness, and the tackiness did not change even in the temperature range of 15 to 30°C, indicating that there was no temperature dependence of tackiness. This was laminated for 12N and heated under the above-mentioned curing conditions to obtain a molded body. Post-impact compressive strength (CA
The results of measuring I) are shown in Table 1.
実施例1,2に示すエポキシ樹脂組成物は粘度が低くプ
リプレグ製造時の作業性が良好であった。The epoxy resin compositions shown in Examples 1 and 2 had low viscosity and good workability during prepreg production.
又、実施例3.4の組成物は製造時の作業性もよく、且
つタック性、ドレープ性、樹脂フロー性、ハンドリング
性、保存安定性等のプリプレグとしての特性も良好で′
あった。実施例5の組成物は、機械加工部品用エポキシ
樹脂として好適なものであった。In addition, the composition of Example 3.4 has good workability during production, and also has good properties as a prepreg such as tackiness, drapeability, resin flowability, handlingability, and storage stability.
there were. The composition of Example 5 was suitable as an epoxy resin for machined parts.
実施例6で得られた組成物はノボラック型の樹脂を配合
した例であるが、他と同様に樹脂物性及びプリプレグ特
性が良好なものであった。The composition obtained in Example 6 was an example in which a novolac type resin was blended, and the resin physical properties and prepreg properties were good like the others.
比較例1〜8
表−1に示す配合”割合にて、上記実施例と同様にして
エポキシ樹脂組成物及びプリプレグ等を作製し試験を行
なった。その結果を表−1に示す。Comparative Examples 1 to 8 Epoxy resin compositions, prepregs, etc. were prepared and tested in the same manner as in the above examples using the formulation ratios shown in Table 1.The results are shown in Table 1.
表−1から各比較例で得られたプリプレグは本発明品に
比較して、タック性、タック安定性(タックの温度依存
性)、保存安定性及び靭性等が悪いことが分る。From Table 1, it can be seen that the prepregs obtained in each comparative example had poorer tackiness, tack stability (temperature dependence of tack), storage stability, and toughness than the products of the present invention.
なお1表−1における硬化剤の記号は次のものを示す。In addition, the symbols of the curing agent in Table 1-1 indicate the following.
(A) C亀NH<H吉E亀
(B) c、H,NH−$馬汁MへH9(C) (A
)/ジシアンジアミド=50150(D)ジシアンジア
ミド
また、実施例2に係るエポキシ樹脂組成物、比較例5の
エポキシ樹脂組成物及び比較例7のエポキシ樹脂組成物
をマトリクス樹脂としたプリプレグのタック性の温度依
存性に関するデータを図面に示す。(A) C turtle NH < H Kichi E turtle (B) c, H, NH-$ Horse soup M to H9 (C) (A
) / dicyandiamide = 50150 (D) dicyandiamide Also, the temperature dependence of the tackiness of prepregs using the epoxy resin composition according to Example 2, the epoxy resin composition of Comparative Example 5, and the epoxy resin composition of Comparative Example 7 as matrix resins. Data regarding sex are shown in the drawing.
図面から、比較例5のようにエポキシ樹脂の数平均分子
量及び重量平均分子量と数平均分子量の比が本発明の範
囲外のものは温度の上昇と共にタック値が低下し、プリ
プレグの粘着性が極端に変化するので操業性が悪いこと
が分る。また、比較例7のようにエポキシ樹脂の数平均
分子量が700を越えると、たとえ重量平均分子量と数
平均分子量が1.3〜3.0の範囲内にあっても、温度
の上昇と共にプリプレグが堅くなり、プリプレグの取り
扱い性が悪くなることが理解される。From the drawings, it can be seen that when the number average molecular weight of the epoxy resin and the ratio of the weight average molecular weight to the number average molecular weight are outside the range of the present invention, as in Comparative Example 5, the tack value decreases as the temperature rises, and the tackiness of the prepreg becomes extremely high. It can be seen that the operability is poor because the temperature changes to . Furthermore, when the number average molecular weight of the epoxy resin exceeds 700 as in Comparative Example 7, even if the weight average molecular weight and number average molecular weight are within the range of 1.3 to 3.0, the prepreg deteriorates as the temperature rises. It is understood that the prepreg becomes hard and the handleability of the prepreg deteriorates.
これに対して、本発明(実施例2)のエポキシ樹脂をマ
トリクスとしたプリプレグは温度が変化してもタック値
はその適正レベルである200〜300gの範囲内にあ
り、その保存性や作業性が良好であることが分る。In contrast, the tack value of the prepreg using the epoxy resin matrix of the present invention (Example 2) remains within the appropriate level of 200 to 300 g even when the temperature changes, and its storage stability and workability are It can be seen that the results are good.
なお、タック値は、溶融樹脂を紙上に30μm程度コー
ティングしたサンプルを10w幅の短冊上にカットし、
このものをタック測定機(東洋精機■製ピクマタック)
の上下2ケのサンプルホールダーに固定し数秒押し付け
た後、一定スピード(20mm/分)で剥離し、その際
の応力をサンプルのタック値とした。The tack value is determined by cutting a sample of paper coated with molten resin to a thickness of about 30 μm onto a 10W strip.
This tack measuring device (Pikmatack manufactured by Toyo Seiki)
The sample was fixed to two upper and lower sample holders, pressed for a few seconds, and then peeled off at a constant speed (20 mm/min), and the stress at that time was taken as the tack value of the sample.
本発明に係るエポキシ樹脂組成物は、耐熱性、弾性率、
硬度、および耐薬品性に優れると共に、特に靭性、可撓
性、衝撃強度に優れた硬化物を与え、破断強度、熱衝撃
に対するクラック性、密着性、接着性にも優れたもので
ある。また、このものを含有するプリプレグは高温下は
もとより常温あるいはそれ以下の温度下においても優れ
たタック性及びドレープ性を示し、しかもこれらの性状
が広い温度範囲に亘って安定に持続するので、作業性や
保存安定性が飛躍的に増大する。The epoxy resin composition according to the present invention has heat resistance, elastic modulus,
In addition to being excellent in hardness and chemical resistance, it provides a cured product with particularly excellent toughness, flexibility, and impact strength, and is also excellent in breaking strength, cracking resistance against thermal shock, adhesion, and adhesion. In addition, prepreg containing this material shows excellent tack and drape properties not only at high temperatures but also at room temperature or lower temperatures, and these properties remain stable over a wide temperature range, making it easy to work with. The properties and storage stability are dramatically increased.
図面は本発明に係るエポキシ樹脂組成物と比較例に係る
エポキシ樹脂組成物をマトリクス樹脂としたプリプレグ
のタック値とタック安定性(タック値の温度依存性)に
ついて比較したグラフである。
特許出願人 東亜燃料工業株式会社The drawing is a graph comparing the tack value and tack stability (temperature dependence of tack value) of prepregs using the epoxy resin composition according to the present invention and the epoxy resin composition according to a comparative example as matrix resins. Patent applicant Toa Fuel Industries Co., Ltd.
Claims (1)
硬化剤とを含有し、前記ビスフェノールA系エポキシ樹
脂は、数平均分子量が450〜700であり、かつその
重量平均分子量と数平均分子量の比(重量平均分子量/
数平均分子量)が1.3〜3.0であり、前記エポキシ
樹脂硬化剤は、下記一般式 HNR_1−A−HNR_2 (式中、R_1及びR_2はアルキル基、シクロアルキ
ル基、アリール基又はアラルキル基を、Aは置換基を有
してもよい二価の脂肪族炭化水素基を表わす) で示されるエポキシ樹脂硬化剤であることを特徴とする
エポキシ樹脂組成物。(1) Contains a bisphenol A-based epoxy resin and an epoxy resin curing agent, and the bisphenol A-based epoxy resin has a number average molecular weight of 450 to 700, and the ratio of the weight average molecular weight to the number average molecular weight (weight average Molecular weight/
number average molecular weight) is 1.3 to 3.0, and the epoxy resin curing agent has the following general formula HNR_1-A-HNR_2 (wherein R_1 and R_2 are an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group). and A represents a divalent aliphatic hydrocarbon group which may have a substituent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25817488A JPH02103223A (en) | 1988-10-12 | 1988-10-12 | Epoxy resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25817488A JPH02103223A (en) | 1988-10-12 | 1988-10-12 | Epoxy resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02103223A true JPH02103223A (en) | 1990-04-16 |
Family
ID=17316554
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25817488A Pending JPH02103223A (en) | 1988-10-12 | 1988-10-12 | Epoxy resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02103223A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5426157A (en) * | 1994-03-16 | 1995-06-20 | Air Products And Chemicals, Inc. | Flexibilized polyepoxide resins incorporating poly-N-methylated secondary amines |
JP2011202158A (en) * | 2010-03-03 | 2011-10-13 | Dainippon Printing Co Ltd | Adhesive composition and method for producing curable pressure-sensitive adhesive sheet |
-
1988
- 1988-10-12 JP JP25817488A patent/JPH02103223A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5426157A (en) * | 1994-03-16 | 1995-06-20 | Air Products And Chemicals, Inc. | Flexibilized polyepoxide resins incorporating poly-N-methylated secondary amines |
JP2011202158A (en) * | 2010-03-03 | 2011-10-13 | Dainippon Printing Co Ltd | Adhesive composition and method for producing curable pressure-sensitive adhesive sheet |
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