JP2579405B2 - Epoxy resin curing agent - Google Patents
Epoxy resin curing agentInfo
- Publication number
- JP2579405B2 JP2579405B2 JP4212303A JP21230392A JP2579405B2 JP 2579405 B2 JP2579405 B2 JP 2579405B2 JP 4212303 A JP4212303 A JP 4212303A JP 21230392 A JP21230392 A JP 21230392A JP 2579405 B2 JP2579405 B2 JP 2579405B2
- Authority
- JP
- Japan
- Prior art keywords
- naphthol
- curing agent
- resin
- epoxy resin
- thermoplastic
- 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
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- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なエポキシ樹脂硬
化剤に係り、特に耐水性、耐湿性、機械的強度等に優れ
た硬化物を与えるエポキシ樹脂硬化剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy resin curing agent, and more particularly to an epoxy resin curing agent which gives a cured product excellent in water resistance, moisture resistance, mechanical strength and the like.
【０００２】[0002]
【従来の技術】近年、特に先端材料分野の進歩に伴い、
より高性能なベースレジンの開発が求められており、例
えば航空宇宙産業で用いられる複合材マトリクス樹脂と
してのエポキシ樹脂については、より一層の高耐熱性、
高耐湿性が要請されている。しかしながら、従来より知
られているエポキシ樹脂にはこれらの要求を満足するも
のは未だ存在しない。例えば、周知のビスフェノールＡ
型エポキシ樹脂は常温で液状であり、作業性に優れてい
ることや、硬化剤、添加剤等との混合が容易であること
から広く使用されているが、耐熱性、耐湿性の点で問題
がある。また、耐熱性を改良したものとしてフェノール
ノボラック型エポキシ樹脂が知られているが、耐湿性や
耐衝撃性に問題がある。さらに、耐衝撃性向上を目的と
してフェノールアラルキル樹脂のエポキシ化合物が提案
されている（特開昭63-238,122号公報）が、このエポキ
シ化合物も耐熱性、耐湿性の点で充分とはいえない。2. Description of the Related Art In recent years, particularly with the advancement of advanced materials,
There is a demand for the development of higher-performance base resins.For example, epoxy resins as composite matrix resins used in the aerospace industry have higher heat resistance,
High moisture resistance is required. However, none of the conventionally known epoxy resins satisfy these requirements. For example, the well-known bisphenol A
Epoxy resins are liquid at room temperature and are widely used because of their excellent workability and easy mixing with hardeners and additives, but they have problems with heat resistance and moisture resistance. There is. A phenol novolak type epoxy resin is known as having improved heat resistance, but has problems in moisture resistance and impact resistance. Further, an epoxy compound of a phenol aralkyl resin has been proposed for the purpose of improving impact resistance (Japanese Patent Application Laid-Open No. 63-238,122), but this epoxy compound is not sufficient in heat resistance and moisture resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、耐熱
性、耐湿性に優れ、かつ、耐衝撃性等の機械的特性にも
優れた性能を有し、積層、成形、注型、接着等の用途に
有用なエポキシ樹脂組成物を調製するための新規なエポ
キシ樹脂硬化剤を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide excellent heat resistance, moisture resistance and mechanical properties such as impact resistance, and to laminate, mold, cast, and bond. Another object of the present invention is to provide a novel epoxy resin curing agent for preparing an epoxy resin composition useful for such uses.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は、下
記一般式（１）That is, the present invention provides a compound represented by the following general formula (1):
【化３】 （但し、式中Ａはナフタレン核を示し、Ｒは水素原子又
はメチル基を示し、ｎは０〜１５の整数を示す）で表さ
れる熱可塑性ナフトールアラルキル樹脂からなるエポキ
シ樹脂硬化剤である。Embedded image (Where A represents a naphthalene nucleus, R represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 15), and is an epoxy resin curing agent comprising a thermoplastic naphthol aralkyl resin.
【０００５】上記一般式（１）で表されるナフトールア
ラルキル樹脂は、１−ナフトール又は２−ナフトールあ
るいはこれらの混合物と、下記一般式（２）[0005] The naphthol aralkyl resin represented by the above general formula (1) is obtained by mixing 1-naphthol or 2-naphthol or a mixture thereof with the following general formula (2)
【化４】 （但し、式中Ｒは水素原子又はメチル基を示し、Ｒ’は
水素原子又は炭素数１〜４の炭化水素基を示す）で表さ
れるジアルコール類又はそのエーテル化合物からなる縮
合剤とを反応させることにより得られる。Embedded image (Wherein, R represents a hydrogen atom or a methyl group, and R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms) with a condensing agent comprising an alcohol or an ether compound thereof. It is obtained by reacting.
【０００６】そして、この縮合剤については、ｏ−体、
ｍ−体、ｐ−体のいずれでもよいが、好ましくはｍ−体
又はｐ−体であり、具体的には、ｐ−キシリレングリコ
ール、α，α’−ジメトキシ−ｐ−キシレン、α，α’
−ジエトキシ−ｐ−キシレン、α，α’−ジ−ｎ−プロ
ポキシ−ｐ−キシレン、α，α’−ジイソプロポキシ−
ｐ−キシレン、１，４−ジ（２−ヒドロキシ−２−プロ
ピル）ベンゼン、１，４−ジ（２−メトキシ−２−プロ
ピル）ベンゼン、１，４−ジ（２−エトキシ−２−プロ
ピル）ベンゼン、１，４−ジ（２−ｎ−プロポキシ−２
−プロピル）ベンゼン、１，４−ジ（２−ｎ−プロポキ
シ−２−プロピル）ベンゼン、１，４−ジ（２−イソプ
ロポキシ−２−プロピル）ベンゼン等が挙げられる。The condensing agent includes an o-isomer,
Any of the m-form and the p-form may be used, but the m-form or the p-form is preferable, and specifically, p-xylylene glycol, α, α′-dimethoxy-p-xylene, α, α '
-Diethoxy-p-xylene, α, α'-di-n- pro
Poxy -p-xylene, α, α'- diisopropoxy-
p-xylene, 1,4-di (2-hydroxy-2-propyl) benzene, 1,4-di (2-methoxy-2-propyl) benzene, 1,4-di (2-ethoxy-2-propyl) Benzene, 1,4-di (2-n-propoxy-2
-Propyl) benzene, 1,4-di (2-n-propoxy-2-propyl) benzene, 1,4-di (2-isopropoxy-2-propyl) benzene, and the like.
【０００７】上記ナフトールと縮合剤とを反応させる際
の両者のモル比は、ナフトール１モルに対して縮合剤が
１モル以下でなければならず、好ましくは０．１〜０．
９の範囲である。０．１モルより少ないと未反応ナフト
ール量が多くなり、樹脂の精製が困難となる。また、
０．９モルを超えると樹脂の軟化点が高くなり、用途に
よっては樹脂の作業性に支障をきたす。The molar ratio of the naphthol and the condensing agent when they are reacted must be not more than 1 mol of the condensing agent to 1 mol of the naphthol, preferably from 0.1 to 0.1 mol.
9 is in the range. If the amount is less than 0.1 mol, the amount of unreacted naphthol increases, and it becomes difficult to purify the resin. Also,
If it exceeds 0.9 mol, the softening point of the resin increases, and the workability of the resin is hindered depending on the application.
【０００８】また、一般式（１）においてｎは１５以下
であることが好ましい。ｎが１５を超えると軟化点が高
くなり、実用上取扱いが困難になるので好ましくない。
同様の理由で、ｎの異なる数種のものを混合物として用
いる場合、ｎ≦４の成分が５０％以上の範囲であること
が好ましい。ｎの分布、すなわち分子量分布は重量平均
分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／
Ｍｎ）で表すことができるが、この場合、この分子量分
布（Ｍｗ／Ｍｎ）は１．１〜２．５の範囲であることが
好ましい。そして、この一般式（１）において、両末端
はナフトール基である必要がある。末端にメチロール基
が残存すると、これをエポキシ樹脂硬化剤として使用し
た場合、得られた樹脂硬化物の耐熱性、耐水性、機械的
強度が大幅に低下するという問題が生じる。In the general formula (1), n is preferably 15 or less. When n exceeds 15, the softening point becomes high and handling becomes difficult in practice, which is not preferable.
For the same reason, when several kinds of compounds having different n are used as a mixture, it is preferable that the component of n ≦ 4 is in a range of 50% or more. The distribution of n, that is, the molecular weight distribution, is a ratio (Mw / Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Mn), and in this case, the molecular weight distribution (Mw / Mn) is preferably in the range of 1.1 to 2.5. In the general formula (1), both terminals need to be naphthol groups. When the methylol group remains at the terminal, when this is used as an epoxy resin curing agent, there arises a problem that the heat resistance, water resistance, and mechanical strength of the obtained resin cured product are significantly reduced.
【０００９】このナフトールと縮合剤とを反応させて熱
可塑性ナフトールアラルキル樹脂を製造する反応は、酸
触媒の存在下に行う。この酸触媒としては、周知の無機
酸、有機酸より適宜選択することができ、例えば、塩
酸、フッ化水素、リン酸、硫酸等の鉱酸や、ギ酸、シュ
ウ酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸等の
有機酸や、塩化亜鉛、塩化アルミニウム等のルイス酸あ
るいは固体酸等が挙げられる。また、反応条件は、反応
温度が通常１０〜２５０℃であって、反応時間が通常１
〜２０時間の範囲である。そして、この反応の際に、メ
タノール、エタノール、プロパノール、ブタノール、エ
チレングリコール、ジエチレングリコール、メチルセロ
ソルブ、エチルセロソルブ等のアルコール類や、ベンゼ
ン、トルエン、クロロベンゼン、ジクロロベンゼン等の
芳香族炭化水素類等の溶媒を使用することもできる。The reaction for producing a thermoplastic naphthol aralkyl resin by reacting this naphthol with a condensing agent is carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, hydrogen fluoride, phosphoric acid, and sulfuric acid, formic acid, oxalic acid, trifluoroacetic acid, p- Examples include organic acids such as toluenesulfonic acid, Lewis acids such as zinc chloride and aluminum chloride, and solid acids. The reaction conditions are such that the reaction temperature is usually 10 to 250 ° C., and the reaction time is usually 1
-20 hours. Then, during this reaction, solvents such as alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, methyl cellosolve, and ethyl cellosolve, and aromatic hydrocarbons such as benzene, toluene, chlorobenzene, and dichlorobenzene. Can also be used.
【００１０】このようにして得られた本発明の熱可塑性
ナフトールアラルキル樹脂は、種々のエポキシ樹脂につ
いてその硬化剤として使用することができる。エポキシ
樹脂硬化剤として使用した場合、従来のフェノールノボ
ラック硬化剤に比べて機械的特性、特に靱性及び耐湿性
に優れた硬化物を得ることができる。[0010] The thermoplastic naphthol aralkyl resin of the present invention thus obtained can be used as a curing agent for various epoxy resins. When used as an epoxy resin curing agent, a cured product excellent in mechanical properties, particularly toughness and moisture resistance, can be obtained as compared with a conventional phenol novolak curing agent.
【００１１】[0011]
【実施例】以下、実施例及び比較例に基づいて、本発明
を具体的に説明する。The present invention will be specifically described below based on examples and comparative examples.
【００１２】実施例１ ５００ｍｌの３口フラスコに１−ナフトール１４４ｇ
（１．０モル）とｐ−キシリレングリコール６９ｇ
（０．５モル）とを１−ブタノール１２０ｍｌに溶解し
て仕込み、さらに水２５ｍｌ及び濃塩酸９．５ｇを加
え、攪拌しながら９５〜９８℃で３時間反応させた。そ
の後、希水酸化ナトリウム水溶液で中和し、水洗した後
１−ブタノールを留去し、さらに未反応１−ナフトール
を水蒸気蒸留により除去し、エポキシ樹脂の中間体とな
る熱可塑性ナフトールアラルキル樹脂１３２ｇを得た。
得られた樹脂のＯＨ当量は２２２であり、ＪＩＳ Ｋ
２５４８法に基づいて測定した軟化点は１０５℃であっ
た。また、得られた樹脂について、そのＧＰＣ、赤外吸
収スペクトル及び 1Ｈ−ＮＭＲを測定した。これらの結
果を図１、図２及び図３に示す。Example 1 144 g of 1-naphthol was placed in a 500 ml three-necked flask.
(1.0 mol) and 69 g of p-xylylene glycol
(0.5 mol) was dissolved in 120 ml of 1-butanol and charged, 25 ml of water and 9.5 g of concentrated hydrochloric acid were added, and the mixture was reacted at 95 to 98 ° C. for 3 hours with stirring. Thereafter, the mixture was neutralized with a dilute sodium hydroxide aqueous solution, washed with water, and then 1-butanol was distilled off. Unreacted 1-naphthol was removed by steam distillation to obtain 132 g of a thermoplastic naphthol aralkyl resin as an intermediate of the epoxy resin. Obtained.
The OH equivalent of the obtained resin was 222 and JIS K
The softening point measured based on the 2548 method was 105 ° C. The GPC, infrared absorption spectrum and 1 H-NMR of the obtained resin were measured. These results are shown in FIGS. 1, 2 and 3.
【００１３】ここで、ＧＰＣの測定は、装置：ＨＬＣ−
８２Ａ〔東ソー（株）製〕及びカラム：ＴＳＫ−ＧＥＬ
２０００×３本及びＴＳＫ−ＧＥＬ４０００×１本〔何
れも東ソー（株）製〕を用い、溶媒：ＴＨＦ、流速：
１．０ｍｌ／分、温度：３８℃、検出器：ＲＩの条件で
行った。このＧＰＣの測定結果から、数平均分子量（Ｍ
ｎ）が５７０、重量平均分子量（Ｍｗ）が８８０であっ
て、分子量分布（Ｍｗ／Ｍｎ）が１．５４であり、ま
た、この実施例１で得られた熱可塑性ナフトールアラル
キル樹脂における一般式（１）のｎの分布は、ｎ＝０が
３５．５％、ｎ＝１が２２．５％、ｎ＝２が１４．５
％、ｎ＝３が９．２％、ｎ＝４が６．９％、及び、ｎ≧
５が１１．４％であった。更に、 1Ｈ−ＮＭＲの測定
は、４００ＭＨｚ核磁気共鳴装置〔日本電子（株）製〕
を用い、プロトンノンデカップリング法により行った。
この 1Ｈ−ＮＭＲの測定結果からこの実施例１で得られ
た熱可塑性ナフトールアラルキル樹脂にはメチロール基
が存在しないことが確認された。Here, the GPC measurement is performed using an apparatus: HLC-
82A (manufactured by Tosoh Corporation) and column: TSK-GEL
Using 2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corporation), solvent: THF, flow rate:
The test was performed under the following conditions: 1.0 ml / min, temperature: 38 ° C., detector: RI. From the GPC measurement results, the number average molecular weight (M
n) is 570, the weight average molecular weight (Mw) is 880, the molecular weight distribution (Mw / Mn) is 1.54, and the thermoplastic naphthol aralkyl resin obtained in Example 1 has the general formula ( In the distribution of n in 1), n = 0 is 35.5%, n = 1 is 22.5%, and n = 2 is 14.5.
%, N = 3 is 9.2%, n = 4 is 6.9%, and n ≧
5 was 11.4%. Further, 1 H-NMR measurement was performed using a 400 MHz nuclear magnetic resonance apparatus [manufactured by JEOL Ltd.].
And using a proton non-decoupling method.
From the 1 H-NMR measurement results, it was confirmed that the thermoplastic naphthol aralkyl resin obtained in Example 1 had no methylol group.
【００１４】実施例２ １−ナフトール９６ｇ（０．６７モル）、ｐ−キシリレ
ングリコール６９ｇ（０．５モル）を用いて実施例１と
同様に反応を行い、熱可塑性ナフトールアラルキル樹脂
１１６ｇを得た。得られた樹脂のＯＨ当量は２３４であ
り、軟化点は１３０℃であった。得られた樹脂のＧＰＣ
を図４に示す。ここで、ＧＰＣの測定条件は実施例１と
同じであり、このＧＰＣの測定結果から、数平均分子量
（Ｍｎ）が７８０、重量平均分子量（Ｍｗ）が１６４０
であって、分子量分布（Ｍｗ／Ｍｎ）が２．１０であ
り、また、この実施例２で得られた熱可塑性ナフトール
アラルキル樹脂における一般式（１）のｎの分布は、ｎ
＝０が１５．２％、ｎ＝１が１６．４％、ｎ＝２が１
３．０％、ｎ＝３が１０．２％、ｎ＝４が８．２％、ｎ
＝５が６．８％、及び、ｎ≧６が３０．２％であった。Example 2 A reaction was conducted in the same manner as in Example 1 using 96 g (0.67 mol) of 1-naphthol and 69 g (0.5 mol) of p-xylylene glycol to obtain 116 g of a thermoplastic naphthol aralkyl resin. Was. The OH equivalent of the obtained resin was 234, and the softening point was 130 ° C. GPC of the obtained resin
Is shown in FIG. Here, the measurement conditions of GPC are the same as those in Example 1. From the measurement results of GPC, the number average molecular weight (Mn) is 780 and the weight average molecular weight (Mw) is 1640.
The molecular weight distribution (Mw / Mn) is 2.10, and the distribution of n in the general formula (1) in the thermoplastic naphthol aralkyl resin obtained in Example 2 is n
= 0, 15.2%, n = 1, 16.4%, n = 2, 1
3.0%, n = 3 10.2%, n = 4 8.2%, n
= 5 was 6.8% and n ≧ 6 was 30.2%.
【００１５】実施例３ ２−ナフトールを用いた以外は、実施例１と全く同様に
して熱可塑性ナフトールアラルキル樹脂１２７．５ｇを
得た。得られた樹脂のＯＨ当量は２２５であり、軟化点
は１１４℃であった。得られた樹脂のＧＰＣを図５に、
また、赤外吸収スペクトルを図６にそれぞれ示す。ここ
で、ＧＰＣの測定条件は実施例１と同じであり、このＧ
ＰＣの測定結果から、数平均分子量（Ｍｎ）が５６０、
重量平均分子量（Ｍｗ）が８５０であって、分子量分布
（Ｍｗ／Ｍｎ）が１．５２であり、また、この実施例３
で得られた熱可塑性ナフトールアラルキル樹脂における
一般式（１）のｎの分布は、ｎ＝０が３６．１％、ｎ＝
１が２３．２％、ｎ＝２が１４．３％、ｎ＝３が９．３
％、ｎ＝４が６．６％、及び、ｎ≧５が１０．６％であ
った。Example 3 127.5 g of a thermoplastic naphthol aralkyl resin was obtained in the same manner as in Example 1 except that 2-naphthol was used. The OH equivalent of the obtained resin was 225, and the softening point was 114 ° C. FIG. 5 shows GPC of the obtained resin.
FIG. 6 shows the infrared absorption spectrum. Here, the measurement conditions of the GPC are the same as those in the first embodiment.
From the measurement results of PC, the number average molecular weight (Mn) was 560,
The weight average molecular weight (Mw) was 850, the molecular weight distribution (Mw / Mn) was 1.52, and
The distribution of n in the general formula (1) in the thermoplastic naphthol aralkyl resin obtained in (3) is such that n = 0 is 36.1%, and n =
1 is 23.2%, n = 2 is 14.3%, and n = 3 is 9.3.
%, N = 4 was 6.6%, and n ≧ 5 was 10.6%.
【００１６】実施例４ ２−ナフトール１４４ｇ（１．０モル）、ｐ−キシリレ
ングリコール４６ｇ（０．３３モル）を１３０℃で加熱
溶解し、ｐ−トルエンスルホン酸０．７ｇを加え、１３
０℃で２時間反応させた。その後、炭酸ナトリウム液で
中和し、さらに未反応２−ナフトールを水蒸気蒸留によ
り除去し、熱可塑性ナフトールアラルキル樹脂６９ｇを
得た。得られた樹脂のＯＨ当量は２１２であり、軟化点
は１０３℃であった。また、実施例１と同じ条件でＧＰ
Ｃを測定した結果、数平均分子量（Ｍｎ）が５３０、重
量平均分子量（Ｍｗ）が６８０であって、分子量分布
（Ｍｗ／Ｍｎ）が１．２８であり、また、この実施例４
で得られた熱可塑性ナフトールアラルキル樹脂における
一般式（１）のｎの分布は、ｎ＝０が４４．７％、ｎ＝
１が２５．９％、ｎ＝２が１３．９％、ｎ＝３が７．１
％、及び、ｎ≧４が８．５％であった。Example 4 144 g (1.0 mol) of 2-naphthol and 46 g (0.33 mol) of p-xylylene glycol were dissolved by heating at 130 ° C., and 0.7 g of p-toluenesulfonic acid was added.
The reaction was performed at 0 ° C. for 2 hours. Thereafter, the mixture was neutralized with a sodium carbonate solution, and unreacted 2-naphthol was removed by steam distillation to obtain 69 g of a thermoplastic naphthol aralkyl resin. The OH equivalent of the obtained resin was 212, and the softening point was 103 ° C. Further, GP was performed under the same conditions as in Example 1.
As a result of measuring C, the number average molecular weight (Mn) was 530, the weight average molecular weight (Mw) was 680, and the molecular weight distribution (Mw / Mn) was 1.28.
The distribution of n in the general formula (1) in the thermoplastic naphthol aralkyl resin obtained in the above is that n = 0 is 44.7%, and n =
1 = 25.9%, n = 2 = 13.9%, n = 3 = 7.1
% And n ≧ 4 were 8.5%.
【００１７】実施例５ ２−ナフトール１０８ｇ（０．７５モル）、ｐ−キシリ
レングリコール６９ｇ（０．５モル）及びシュウ酸５．
４ｇを仕込み、１５０℃で６時間反応を行った。この間
に生成した水は系外に除去した。その後、未反応２−ナ
フトールは水蒸気蒸留により除去し、熱可塑性ナフトー
ルアラルキル樹脂１１９ｇを得た。得られた樹脂のＯＨ
当量は２２３．５であり、軟化点は１３６℃であった。
また、実施例１と同じ条件でＧＰＣを測定した結果、数
平均分子量（Ｍｎ）が６６０、重量平均分子量（Ｍｗ）
が１１４０であって、分子量分布（Ｍｗ／Ｍｎ）が１．
７３であり、また、この実施例５で得られた熱可塑性ナ
フトールアラルキル樹脂における一般式（１）のｎの分
布は、ｎ＝０が２８．８％、ｎ＝１が１９．４％、ｎ＝
２が１４．１％、ｎ＝３が１０．３％、ｎ＝４が７．８
％、及び、ｎ≧５が２０．４％であった。Example 5 108 g (0.75 mol) of 2-naphthol, 69 g (0.5 mol) of p-xylylene glycol and oxalic acid5.
4 g was charged and reacted at 150 ° C. for 6 hours. Water generated during this time was removed outside the system. Thereafter, unreacted 2-naphthol was removed by steam distillation to obtain 119 g of a thermoplastic naphthol aralkyl resin. OH of the obtained resin
The equivalent weight was 223.5 and the softening point was 136 ° C.
GPC was measured under the same conditions as in Example 1. As a result, the number average molecular weight (Mn) was 660, and the weight average molecular weight (Mw).
Is 1140 and the molecular weight distribution (Mw / Mn) is 1.
The distribution of n in the general formula (1) in the thermoplastic naphthol aralkyl resin obtained in Example 5 is such that n = 0 is 28.8%, n = 1 is 19.4%, and n is 19.4%. =
2 is 14.1%, n = 3 is 10.3%, and n = 4 is 7.8.
% And n ≧ 5 were 20.4%.
【００１８】試験例１ ｏ−クレゾールノボラック型エポキシ樹脂１００重量部
に対し、エポキシ樹脂硬化剤として実施例５で得られた
ナフトールアラルキル樹脂を１１４重量部と、硬化促進
剤としてトリフェニルホスフィン３重量部とを配合して
エポキシ樹脂組成物を調製した。このエポキシ樹脂組成
物を１５０℃で成形し、得られたエポキシ硬化物を試験
片として各種の物性を測定した。結果を表１に示す。な
お、ガラス転移点及び線膨張係数は熱機械分析装置を使
用して７℃／分の昇温速度で測定した。曲げ強度と曲げ
弾性率はＪＩＳ Ｋ ６９１１法に準じて測定した。ま
た、吸水率は１３３℃、３気圧の条件で１００時間吸湿
させて測定した。さらに、破壊靱性はA. F. Yee, R. A.
Pearson, Journal of Materials Science, 21, 2462(1
986)に記載の方法に従って測定した。Test Example 1 Based on 100 parts by weight of o-cresol novolak type epoxy resin, 114 parts by weight of the naphthol aralkyl resin obtained in Example 5 as an epoxy resin curing agent, and 3 parts by weight of triphenylphosphine as a curing accelerator. And an epoxy resin composition was prepared. This epoxy resin composition was molded at 150 ° C., and various physical properties were measured using the obtained epoxy cured product as a test piece. Table 1 shows the results. The glass transition point and the coefficient of linear expansion were measured at a heating rate of 7 ° C./min using a thermomechanical analyzer. Flexural strength and flexural modulus were measured according to JIS K 6911 method. The water absorption was measured at 133 ° C. and 3 atm for 100 hours. Furthermore, the fracture toughness is AF Yee, RA
Pearson, Journal of Materials Science, 21 , 2462 (1
986).
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】本発明より得られるナフトールアラルキ
ル樹脂は、これを種々のエポキシ樹脂の硬化剤として使
用した場合、耐熱性、耐湿性及び耐衝撃性に優れた硬化
物を与えることができ、極めて有用である。The naphthol aralkyl resin obtained according to the present invention, when used as a curing agent for various epoxy resins, can give a cured product having excellent heat resistance, moisture resistance and impact resistance. Useful.
【図１】 図１は実施例１で得られた樹脂のＧＰＣを示
すグラフ図である。FIG. 1 is a graph showing GPC of the resin obtained in Example 1.
【図２】 図２は実施例１で得られた樹脂の赤外吸収ス
ペクトルを示すグラフ図である。FIG. 2 is a graph showing an infrared absorption spectrum of the resin obtained in Example 1.
【図３】 図３は実施例１で得られた樹脂の 1Ｈ−ＮＭ
Ｒを示すグラフ図である。FIG. 3 shows 1 H-NM of the resin obtained in Example 1.
It is a graph which shows R.
【図４】 図４は実施例２で得られた樹脂のＧＰＣを示
すグラフ図である。FIG. 4 is a graph showing GPC of the resin obtained in Example 2.
【図５】 図５は実施例３で得られた樹脂のＧＰＣを示
すグラフ図である。FIG. 5 is a graph showing GPC of the resin obtained in Example 3.
【図６】 図６は、実施例３で得られた樹脂の赤外吸収
スペクトルを示すグラフ図である。FIG. 6 is a graph showing an infrared absorption spectrum of the resin obtained in Example 3.
Claims (2)
はメチル基を示し、ｎは０〜１５の整数を示す）で表さ
れる熱可塑性ナフトールアラルキル樹脂からなるエポキ
シ樹脂硬化剤。[Claim 1] The following general formula (1) (Where A represents a naphthalene nucleus, R represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 15), an epoxy resin curing agent comprising a thermoplastic naphthol aralkyl resin.
ールアラルキル樹脂が、ナフトールと下記一般式（２） 【化２】 （但し、式中Ｒは水素原子又はメチル基を示し、Ｒ’は
水素原子又は炭素数１〜４の炭化水素基を示す）で表さ
れる縮合剤とを、ナフトール１モルに対して縮合剤を
０．１〜０．９モルの割合で、かつ、末端にメチロール
基が残存しない条件で反応させて得られたものである請
求項１記載のエポキシ樹脂硬化剤。2. A thermoplastic naphthol aralkyl resin represented by the general formula (1) is formed by combining naphthol with the following general formula (2). (Wherein, R represents a hydrogen atom or a methyl group, and R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms) with a condensing agent per 1 mol of naphthol. The epoxy resin curing agent according to claim 1, which is obtained by reacting at a ratio of 0.1 to 0.9 mol and under the condition that no methylol group remains at the terminal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4212303A JP2579405B2 (en) | 1992-07-17 | 1992-07-17 | Epoxy resin curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4212303A JP2579405B2 (en) | 1992-07-17 | 1992-07-17 | Epoxy resin curing agent |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1224520A Division JPH0390075A (en) | 1989-09-01 | 1989-09-01 | Epoxy resin, its intermediate and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05214076A JPH05214076A (en) | 1993-08-24 |
| JP2579405B2 true JP2579405B2 (en) | 1997-02-05 |
Family
ID=16620341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4212303A Expired - Lifetime JP2579405B2 (en) | 1992-07-17 | 1992-07-17 | Epoxy resin curing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2579405B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5165816B2 (en) * | 2000-03-14 | 2013-03-21 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product thereof |
| JP2006056969A (en) * | 2004-08-19 | 2006-03-02 | Nippon Steel Chem Co Ltd | Epoxy resin composition and cured product thereof |
| JP6090765B2 (en) * | 2012-07-02 | 2017-03-08 | 日本化薬株式会社 | Phenol resin, epoxy resin, and curable resin composition |
| KR20210146339A (en) * | 2019-03-27 | 2021-12-03 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Naphthol resin, epoxy resin, epoxy resin composition and cured product thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS521760A (en) * | 1975-06-24 | 1977-01-07 | Nittetsu Mining Co Ltd | Device of automatically detecting the level of sludge in a centrifugal separator |
| JPS6115882A (en) * | 1984-07-02 | 1986-01-23 | Hokuriku Seiyaku Co Ltd | N-acyl-2,6-xylidine derivative |
| JPS6228165A (en) * | 1985-07-29 | 1987-02-06 | Kobe Steel Ltd | Polishing method |
-
1992
- 1992-07-17 JP JP4212303A patent/JP2579405B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS521760A (en) * | 1975-06-24 | 1977-01-07 | Nittetsu Mining Co Ltd | Device of automatically detecting the level of sludge in a centrifugal separator |
| JPS6115882A (en) * | 1984-07-02 | 1986-01-23 | Hokuriku Seiyaku Co Ltd | N-acyl-2,6-xylidine derivative |
| JPS6228165A (en) * | 1985-07-29 | 1987-02-06 | Kobe Steel Ltd | Polishing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05214076A (en) | 1993-08-24 |
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