JPH07179399A - (methyl)nadic acid half ester and crosslinking agent - Google Patents
(methyl)nadic acid half ester and crosslinking agentInfo
- Publication number
- JPH07179399A JPH07179399A JP31658993A JP31658993A JPH07179399A JP H07179399 A JPH07179399 A JP H07179399A JP 31658993 A JP31658993 A JP 31658993A JP 31658993 A JP31658993 A JP 31658993A JP H07179399 A JPH07179399 A JP H07179399A
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- JP
- Japan
- Prior art keywords
- methyl
- parts
- acid anhydride
- half ester
- acid
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、加熱により容易に酸無
水物を形成する新規なジカルボン酸ハーフエステルに関
するものであり、さらに詳しくは熱硬化性樹脂の架橋剤
に好適なジカルボン酸ハーフエステルに関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dicarboxylic acid half ester which easily forms an acid anhydride upon heating, and more specifically to a dicarboxylic acid half ester suitable as a crosslinking agent for thermosetting resins. It is a thing.
【０００２】[0002]
【従来の技術】一般に、メラミン樹脂やポリイソシアネ
ート化合物を架橋剤とする熱硬化性樹脂は、耐候性、美
粧性に優れた性能を有することから広範な用途で種々使
用されている。しかし、メラミン樹脂を架橋剤として使
用すると耐酸性が低下し、例えばこれを塗料に適用した
場合、酸性雨により塗膜に雨ジミが発生し、外観が低下
するという欠点を有する。一方、ポリイソシアネート化
合物を架橋剤として使用した場合、ポリイソシアネート
化合物の持つ毒性が、作業者の健康に悪影響を及ぼす等
の環境上の問題が指摘されている。2. Description of the Related Art Generally, a thermosetting resin containing a melamine resin or a polyisocyanate compound as a cross-linking agent is used in a wide variety of applications because of its excellent weather resistance and beauty. However, when a melamine resin is used as a cross-linking agent, the acid resistance is lowered. For example, when this is applied to a paint, there is a drawback that acid rain causes a rain stain on the coating film and the appearance is deteriorated. On the other hand, it has been pointed out that when a polyisocyanate compound is used as a cross-linking agent, the toxicity of the polyisocyanate compound adversely affects the health of workers and other environmental problems.
【０００３】これらの問題を解決するために、メラミン
樹脂やポリイソシアネート化合物に代わる、熱硬化型塗
料用架橋剤が求められており、酸基とエポキシ基の硬化
反応を利用した架橋剤等の検討が盛んに行われている。
例えば、特開昭６３−８４６７４号公報には、接着性、
光沢および鮮映性に優れた塗料用組成物として、低分子
量ポリエポキシド、低分子量ヒドロキシル基含有多官能
性物質、酸無水物からなる架橋剤および硬化触媒を含有
する高固形分硬化性組成物が開示されている。In order to solve these problems, a cross-linking agent for thermosetting paints, which is an alternative to the melamine resin and the polyisocyanate compound, is required, and a cross-linking agent utilizing a curing reaction between an acid group and an epoxy group is examined. Is being actively conducted.
For example, in JP-A-63-84674, adhesiveness,
Disclosed is a high solids curable composition containing a low molecular weight polyepoxide, a low molecular weight hydroxyl group-containing polyfunctional substance, a cross-linking agent composed of an acid anhydride, and a curing catalyst as a coating composition having excellent gloss and sharpness. Has been done.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記のような
酸無水物からなる架橋剤は、化学的活性が強いため刺激
性を有し、作業環境を損なう等の問題点を有しており、
また、組成成分間の反応性が高くなるために貯蔵安定性
が悪く、組成成分全体を一液化することが困難であり、
作業性が悪いという問題点を有していた。However, the above-mentioned cross-linking agent composed of an acid anhydride has a strong chemical activity and is irritating and has a problem that the working environment is impaired.
Further, since the reactivity between the composition components becomes high, the storage stability is poor, and it is difficult to liquefy the entire composition components.
It had a problem of poor workability.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記従来
技術の問題点に鑑み、熱硬化性型樹脂用架橋剤ついて鋭
意検討した結果、特定のジカルボン酸無水物前駆体が、
加熱により容易にジカルボン酸無水物を形成することを
見いだし、本発明に至ったものである。すなわち、本発
明の第一の発明である（メチル）ナジック酸ハーフエス
テルは、次の一般式（１）で示されるものである。DISCLOSURE OF THE INVENTION In view of the above-mentioned problems of the prior art, the inventors of the present invention have diligently studied a crosslinking agent for a thermosetting resin, and as a result, a specific dicarboxylic acid anhydride precursor was found to be
It was found that the dicarboxylic acid anhydride is easily formed by heating, and the present invention has been completed. That is, the (methyl) naphthic acid half ester, which is the first invention of the present invention, is represented by the following general formula (1).
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】（式中、Ｒは水素またはメチル基であり、
ｎは１〜４の整数である。）また、本発明の第二の発明
である熱硬化性樹脂用架橋剤は、上記一般式（１）で示
される（メチル）ナジック酸ハーフエステルからなるこ
とを特徴とするものである。なお、本発明において、
（メチル）ナジック酸はナジック酸あるいはメチルナジ
ック酸を示す。(Wherein R is hydrogen or a methyl group,
n is an integer of 1 to 4. ) Further, the crosslinking agent for thermosetting resin, which is the second invention of the present invention, is characterized by comprising a (methyl) nadic acid half ester represented by the above general formula (1). In the present invention,
(Methyl) nadic acid means nadic acid or methyl nadic acid.
【０００８】本発明の（メチル）ナジック酸ハーフエス
テルは、無水（メチル）ナジック酸と一価アルコール類
を無触媒または塩基性触媒存在下で反応させることによ
り合成することができる。一価アルコールとしては、例
えば、メチルアルコール、エチルアルコール、ｎ−プロ
ピルアルコール、イソプロピルアルコール、ｎ−ブチル
アルコール、イソブチルアルコール、ｔ−ブチルアルコ
ール等の炭素数が１〜４である一価アルコール類が使用
できる。本発明においては、一価アルコール類として炭
素数が１〜４であることが、すなわち上記一般式（１）
においてｎが１〜４であることが重要である。これは、
一価アルコール類の炭素数が５以上になると、得られた
（メチル）ナジック酸ハーフエステルの酸無水物への変
化率が７０％未満に低下するためである。The (methyl) naphthic acid half ester of the present invention can be synthesized by reacting (methyl) naphthic acid anhydride with a monohydric alcohol in the absence of a catalyst or a basic catalyst. As the monohydric alcohol, for example, monohydric alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and t-butyl alcohol are used. it can. In the present invention, the monohydric alcohols having 1 to 4 carbon atoms, that is, the above-mentioned general formula (1)
It is important that n is 1 to 4. this is,
This is because when the number of carbon atoms in the monohydric alcohol is 5 or more, the conversion rate of the obtained (methyl) naphthic acid half ester to the acid anhydride decreases to less than 70%.
【０００９】また、塩基性触媒としては、例えば、トリ
エチルアミン、トリブチルアミン、ジメチルアニリン等
のアミン類が好適である。反応物のモル比は、無水（メ
チル）ナジック酸：一価アルコール類＝１：１〜１：２
０の範囲であり、好ましくは１：２〜１：１０である。
塩基性触媒を使用する場合には、その添加量は無水（メ
チル）ナジック酸に対して０．１〜２００モルパーセン
ト、好ましくは１〜１００モルパーセントである。ま
た、反応温度は、無触媒の場合では４０〜１００℃、好
ましくは６０〜８０℃であり、塩基性触媒を使用する場
合には０〜８０℃、好ましくは２０〜５０℃である。As the basic catalyst, amines such as triethylamine, tributylamine and dimethylaniline are suitable. The molar ratio of the reactants is (methyl) nadic acid anhydride: monohydric alcohols = 1: 1 to 1: 2.
The range is 0, preferably 1: 2 to 1:10.
When a basic catalyst is used, its addition amount is 0.1 to 200 mol%, preferably 1 to 100 mol% based on (methyl) naphthic anhydride. Further, the reaction temperature is 40 to 100 ° C, preferably 60 to 80 ° C in the case of no catalyst, and 0 to 80 ° C, preferably 20 to 50 ° C in the case of using a basic catalyst.
【００１０】このようにして得られた本発明の（メチ
ル）ナジック酸ハーフエステルは、常温では化学的活性
が低く、低臭気、低刺激性であり、加熱時においても有
毒な蒸気を発生しない。また、加熱によって容易に酸無
水物を形成するために化学的活性が高くなるものであ
る。本発明の（メチル）ナジック酸ハーフエステルは、
上記のような特徴を有しており、エポキシ基含有樹脂等
に代表される熱硬化性樹脂の架橋剤として使用すると、
貯蔵安定性が極めて良好であるために、これら組成物全
体の一液化が可能となり、特に、塗料、接着剤等に使用
される熱硬化性樹脂の架橋剤として非常に有効なもので
ある。The thus-obtained (methyl) naphthic acid half ester of the present invention has low chemical activity at room temperature, low odor and low irritation, and does not generate toxic vapor even when heated. Further, the chemical activity is increased because an acid anhydride is easily formed by heating. The (methyl) naphthic acid half ester of the present invention is
It has the above characteristics, and when used as a cross-linking agent for thermosetting resins typified by epoxy group-containing resins,
Since it has extremely good storage stability, it can be made into a liquefied composition as a whole, and is particularly effective as a crosslinking agent for thermosetting resins used in paints, adhesives and the like.
【００１１】本発明の（メチル）ナジック酸ハーフエス
テルを熱硬化性樹脂用架橋剤として使用する場合には、
酸無水物への変化率が７０％以上であることが好まし
く、より好ましくは８０％以上である。酸無水物への変
化率が７０％未満であると、樹脂の硬化性が損なわれる
傾向にあり好ましくない。When the (methyl) naphthic acid half ester of the present invention is used as a crosslinking agent for thermosetting resins,
The rate of conversion to an acid anhydride is preferably 70% or more, more preferably 80% or more. When the rate of conversion to acid anhydride is less than 70%, the curability of the resin tends to be impaired, which is not preferable.
【００１２】[0012]
【実施例】以下、本発明を製造例、実施例、比較例を挙
げて具体的に説明する。例中の部は、全て重量基準であ
る。 ・ハーフエステルから酸無水物への変化率の評価方法 ハーフエステルを岩塩板に塗布したものを１４０℃で３
０分間保持した時における、ハーフエステルから酸無水
物への変化率を赤外吸収スペクトルによって測定した
（カルボキシル基の特性吸収（２４００〜３４００ｃｍ
-1）が消失し、酸無水物基の特性吸収（１７８０ｃ
ｍ-1、１８６０ｃｍ-1）が発生する。）。EXAMPLES The present invention will be specifically described below with reference to production examples, examples and comparative examples. All parts in the examples are by weight.・ Evaluation method of rate of change from half-ester to acid anhydride Half-ester coated on rock salt plate at 140 ° C for 3
The rate of change from a half ester to an acid anhydride when it was held for 0 minute was measured by infrared absorption spectrum (characteristic absorption of carboxyl group (2400-3400 cm
-1 ) disappears and the characteristic absorption of the acid anhydride group (1780c
m -1 , 1860 cm -1 ) is generated. ).
【００１３】・塗膜性能の定義 鉛筆硬度：ＪＩＳ Ｋ−５４００の「鉛筆引っかき試
験」に準じた。 貯蔵安定性：実施例、比較例で調製した樹脂組成物を５
０℃で一週間保存した後の状態の変化で判断した。Definition of coating film performance Pencil hardness: According to JIS K-5400 "pencil scratch test". Storage stability: The resin compositions prepared in Examples and Comparative Examples were 5
Judgment was made based on the change in state after storage at 0 ° C for one week.
【００１４】製造例１ 温度計、攪拌機、コンデンサー、温度制御装置を備えた
四つ口フラスコに、無水ナジック酸（日本化薬（株）
製、カヤハードＣＤ）１６４部、メタノール１６０部を
仕込み、７０℃で６時間反応させた。赤外吸収スペクト
ル測定で、酸無水物基の吸収特性（１７８０ｃｍ-1、１
８６０ｃｍ-1）が消失し、カルボキシル基の吸収特性
（２４００〜３４００ｃｍ-1）が発生していることを確
認した後、過剰のメタノールを減圧留去し、白色固体の
ナジック酸モノメチルエステル（Ｈ−１）を得た。得ら
れたハーフエステルの酸無水物への変化率は９５％以上
であった。Production Example 1 A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature control device was charged with nadic acid anhydride (Nippon Kayaku Co., Ltd.).
(Manufactured by Kayahard CD) and 160 parts of methanol were charged and reacted at 70 ° C. for 6 hours. Infrared absorption spectrum measurement showed that the absorption characteristics of the acid anhydride group (1780 cm -1 , 1,
860 cm −1 ) disappeared and it was confirmed that the absorption characteristics of the carboxyl group (2400 to 3400 cm −1 ) had occurred, and then excess methanol was distilled off under reduced pressure to obtain a white solid of nadic acid monomethyl ester (H- 1) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 95% or more.
【００１５】製造例２ 温度計、攪拌機、コンデンサー、温度制御装置を備えた
四つ口フラスコに、無水メチルナジック酸（日本化薬
（株）製、カヤハードＭＣＤ）１７８部、メタノール１
６０部を仕込み、７０℃で６時間反応させた。赤外吸収
スペクトル測定で、酸無水物基の吸収特性（１７８０ｃ
ｍ-1、１８６０ｃｍ-1）が消失し、カルボキシル基の吸
収特性（２４００〜３４００ｃｍ-1）が発生しているこ
とを確認した後、過剰のメタノールを減圧留去し、淡黄
色液体のメチルナジック酸モノメチルエステル（Ｈ−
２）を得た。得られたハーフエステルの酸無水物への変
化率は９５％以上であった。Production Example 2 In a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature control device, 178 parts of methylnadic acid anhydride (Kayahard MCD manufactured by Nippon Kayaku Co., Ltd.) and 1 methanol
60 parts were charged and the reaction was carried out at 70 ° C. for 6 hours. Infrared absorption spectrum measurement showed absorption characteristics of acid anhydride group (1780c
m -1 , 1860 cm -1 ) disappeared, and it was confirmed that the absorption property of the carboxyl group (2400-3400 cm -1 ) had occurred, and then excess methanol was distilled off under reduced pressure to obtain a pale yellow liquid methyl nazic. Acid monomethyl ester (H-
2) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 95% or more.
【００１６】製造例３ 温度計、攪拌機、コンデンサー、温度制御装置を備えた
四つ口フラスコに、無水メチルナジック酸（日本化薬
（株）製、カヤハードＭＣＤ）１７８部、エタノール２
３０部を仕込み、７０℃で６時間反応させた。赤外吸収
スペクトル測定で、酸無水物基の吸収特性（１７８０ｃ
ｍ-1、１８６０ｃｍ-1）が消失し、カルボキシル基の吸
収特性（２４００〜３４００ｃｍ-1）が発生しているこ
とを確認した後、過剰のエタノールを減圧留去し、淡黄
色液体のメチルナジック酸モノエチルエステル（Ｈ−
３）を得た。得られたハーフエステルの酸無水物への変
化率は９０％であった。Production Example 3 In a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature controller, 178 parts of methylnadic acid anhydride (Kayahard MCD manufactured by Nippon Kayaku Co., Ltd.) and ethanol 2
30 parts were charged and reacted at 70 ° C. for 6 hours. Infrared absorption spectrum measurement showed absorption characteristics of acid anhydride group (1780c
m -1 , 1860 cm -1 ) disappeared, and after confirming that the absorption characteristics of the carboxyl group (2400-3400 cm -1 ) were generated, excess ethanol was distilled off under reduced pressure, and a pale yellow liquid methylnazic was obtained. Acid monoethyl ester (H-
3) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 90%.
【００１７】製造例４ 温度計、攪拌機、コンデンサー、温度制御装置を備えた
四つ口フラスコに、無水メチルナジック酸（日本化薬
（株）製、カヤハードＭＣＤ）１７８部、ｎ−プロパノ
ール３００部を仕込み、７０℃で６時間反応させた。赤
外吸収スペクトル測定で、酸無水物基の吸収特性（１７
８０ｃｍ-1、１８６０ｃｍ-1）が消失し、カルボキシル
基の吸収特性（２４００〜３４００ｃｍ-1）が発生して
いることを確認した後、過剰のｎ−プロパノールを減圧
留去し、淡黄色液体のメチルナジック酸モノプロピルエ
ステル（Ｈ−４）を得た。得られたハーフエステルの酸
無水物への変化率は８５％であった。Production Example 4 In a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature control device, 178 parts of methyl nadic acid anhydride (Kayahard MCD manufactured by Nippon Kayaku Co., Ltd.) and 300 parts of n-propanol were placed. After charging, the mixture was reacted at 70 ° C. for 6 hours. Infrared absorption spectrum measurement showed that the absorption characteristics of the acid anhydride group (17
80 cm -1, 1860 cm -1) disappeared, after confirming that the absorption characteristics of the carboxyl group (2400~3400cm -1) is generated, and evaporated under reduced pressure and excess n- propanol, pale yellow liquid Methyl nadic acid monopropyl ester (H-4) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 85%.
【００１８】製造例５ 温度計、攪拌機、コンデンサー、温度制御装置を備えた
四つ口フラスコに、無水メチルナジック酸（日本化薬
（株）製、カヤハードＭＣＤ）１７８部、ｎ−ブタノー
ル３７０部を仕込み、７０℃で６時間反応させた。赤外
吸収スペクトル測定で、酸無水物基の吸収特性（１７８
０ｃｍ-1、１８６０ｃｍ-1）が消失し、カルボキシル基
の吸収特性（２４００〜３４００ｃｍ-1）が発生してい
ることを確認した後、過剰のｎ−ブタノールを減圧留去
し、淡黄色液体のメチルナジック酸モノブチルエステル
（Ｈ−５）を得た。得られたハーフエステルの酸無水物
への変化率は７５％であった。Production Example 5 In a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature controller, 178 parts of methylnadic acid anhydride (Kayahard MCD manufactured by Nippon Kayaku Co., Ltd.) and 370 parts of n-butanol were placed. After charging, the mixture was reacted at 70 ° C. for 6 hours. Infrared absorption spectrum measurement showed that the absorption characteristics of the acid anhydride group (178
0 cm -1, 1860 cm -1) disappeared, after confirming that the absorption characteristics of the carboxyl group (2400~3400cm -1) is generated, and evaporated under reduced pressure and excess n- butanol, pale yellow liquid Methyl nadic acid monobutyl ester (H-5) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 75%.
【００１９】製造例６ 温度計、攪拌機、コンデンサー、温度制御装置を備えた
四つ口フラスコに、無水メチルナジック酸（日本化薬
（株）製、カヤハードＭＣＤ）１７８部、ｎ−ヘキサノ
ール１５３部を仕込み、７０℃で６時間反応させた。赤
外吸収スペクトル測定で、酸無水物基の吸収特性（１７
８０ｃｍ-1、１８６０ｃｍ-1）が消失し、カルボキシル
基の吸収特性（２４００〜３４００ｃｍ-1）が発生して
いることを確認した後、過剰のｎ−ヘキサノール（Ｈ−
６）を減圧留去し、淡黄色液体のメチルナジック酸モノ
ヘキシルエステルを得た。得られたハーフエステルの酸
無水物への変化率は４０％であった。Production Example 6 In a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature controller, 178 parts of methylnadic acid anhydride (Kayahard MCD manufactured by Nippon Kayaku Co., Ltd.) and 153 parts of n-hexanol were placed. After charging, the mixture was reacted at 70 ° C. for 6 hours. Infrared absorption spectrum measurement showed that the absorption characteristics of the acid anhydride group (17
80 cm -1, 1860 cm -1) disappeared, after the absorption characteristics of the carboxyl group (2400~3400cm -1) it was confirmed that has occurred, excess n- hexanol (H-
6) was distilled off under reduced pressure to obtain methyl nadic acid monohexyl ester as a pale yellow liquid. The rate of conversion of the obtained half ester to an acid anhydride was 40%.
【００２０】実施例１ ナジック酸モノメチルエステル（Ｈ−１）２０部に、エ
ポキシ樹脂（東都化成（株）製、エポトートＹＤ−１２
８）１９部、臭化テトラブチルアンモニウム０．７８部
を配合して樹脂組成物を調製した。得られた樹脂組成物
の貯蔵安定性は良好であった。この樹脂組成物を希釈
（溶剤：キシレン、固形分：６０％）し、これをバーコ
ーターで水研板に塗布した後、１４０℃で３０分間焼き
付けた。得られた塗膜の鉛筆硬度はＨであった。Example 1 20 parts of nadic acid monomethyl ester (H-1) was mixed with an epoxy resin (Epototo YD-12 manufactured by Tohto Kasei Co., Ltd.).
8) 19 parts and 0.78 part of tetrabutylammonium bromide were mixed to prepare a resin composition. The storage stability of the obtained resin composition was good. This resin composition was diluted (solvent: xylene, solid content: 60%), applied to a water-inspecting plate with a bar coater, and then baked at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was H.
【００２１】実施例２ メチルナジック酸モノメチルエステル（Ｈ−２）２１部
に、エポキシ樹脂（東都化成（株）製、エポトートＹＤ
−１２８）１９部、臭化テトラブチルアンモニウム０．
８部を配合して樹脂組成物を調製した。得られた樹脂組
成物の貯蔵安定性は良好であった。この樹脂組成物を希
釈（溶剤：キシレン、固形分：６０％）し、これをバー
コーターで水研板に塗布した後、１４０℃で３０分間焼
き付けた。得られた塗膜の鉛筆硬度はＨであった。Example 2 To 21 parts of methyl nadic acid monomethyl ester (H-2) was added an epoxy resin (Epototo YD manufactured by Tohto Kasei Co., Ltd.).
-128) 19 parts, tetrabutylammonium bromide 0.
A resin composition was prepared by mixing 8 parts. The storage stability of the obtained resin composition was good. This resin composition was diluted (solvent: xylene, solid content: 60%), applied to a water-inspecting plate with a bar coater, and then baked at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was H.
【００２２】実施例３ メチルナジック酸モノエチルエステル（Ｈ−３）２２部
に、エポキシ樹脂（東都化成（株）製、エポトートＹＤ
−１２８）１９部、臭化テトラブチルアンモニウム０．
８２部を配合して樹脂組成物を調製した。得られた樹脂
組成物の貯蔵安定性は良好であった。この樹脂組成物を
希釈（溶剤：キシレン、固形分：６０％）し、これをバ
ーコーターで水研板に塗布した後、１４０℃で３０分間
焼き付けた。得られた塗膜の鉛筆硬度はＦであった。Example 3 22 parts of methyl nadic acid monoethyl ester (H-3) was mixed with an epoxy resin (Epototo YD manufactured by Tohto Kasei Co., Ltd.).
-128) 19 parts, tetrabutylammonium bromide 0.
82 parts were blended to prepare a resin composition. The storage stability of the obtained resin composition was good. This resin composition was diluted (solvent: xylene, solid content: 60%), applied to a water-inspecting plate with a bar coater, and then baked at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was F.
【００２３】実施例４ メチルナジック酸モノプロピルエステル（Ｈ−４）２４
部に、エポキシ樹脂（東都化成（株）製、エポトートＹ
Ｄ−１２８）１９部、臭化テトラブチルアンモニウム
０．８６部を配合して樹脂組成物を調製した。得られた
樹脂組成物の貯蔵安定性は良好であった。この樹脂組成
物を希釈（溶剤：キシレン、固形分：６０％）し、これ
をバーコーターで水研板に塗布した後、１４０℃で３０
分間焼き付けた。得られた塗膜の鉛筆硬度はＨＢであっ
た。Example 4 Methyl nadic acid monopropyl ester (H-4) 24
Epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epotote Y)
D-128) 19 parts and tetrabutylammonium bromide 0.86 parts were blended to prepare a resin composition. The storage stability of the obtained resin composition was good. This resin composition was diluted (solvent: xylene, solid content: 60%) and applied to a water-inspecting plate with a bar coater, then at 30 ° C. at 30 ° C.
Baked for a minute. The pencil hardness of the obtained coating film was HB.
【００２４】実施例５ メチルナジック酸モノブチルエステル（Ｈ−５）２５部
に、エポキシ樹脂（東都化成（株）製、エポトートＹＤ
−１２８）１９部、臭化テトラブチルアンモニウム０．
８８部を配合して樹脂組成物を調製した。得られた樹脂
組成物の貯蔵安定性は良好であった。この樹脂組成物を
希釈（溶剤：キシレン、固形分：６０％）し、これをバ
ーコーターで水研板に塗布した後、１４０℃で３０分間
焼き付けた。得られた塗膜の鉛筆硬度はＨＢであった。Example 5 25 parts of methyl naphthic acid monobutyl ester (H-5) was mixed with an epoxy resin (Epototo YD manufactured by Tohto Kasei Co., Ltd.).
-128) 19 parts, tetrabutylammonium bromide 0.
A resin composition was prepared by mixing 88 parts. The storage stability of the obtained resin composition was good. This resin composition was diluted (solvent: xylene, solid content: 60%), applied to a water-inspecting plate with a bar coater, and then baked at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was HB.
【００２５】比較例１ メチルナジック酸モノヘキシルエステル（Ｈ−６）２２
部に、エポキシ樹脂（東都化成（株）製、エポトートＹ
Ｄ−１２８）１９部、臭化テトラブチルアンモニウム
０．９２部を配合して樹脂組成物を調製した。得られた
樹脂組成物の貯蔵安定性は良好であった。この樹脂組成
物を希釈（溶剤：キシレン、固形分：６０％）し、これ
をバーコーターで水研板に塗布した後１４０℃で３０分
間処理したが樹脂が硬化せず塗膜が得られなかった。Comparative Example 1 Methyl nadic acid monohexyl ester (H-6) 22
Epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epotote Y)
D-128) 19 parts and tetrabutylammonium bromide 0.92 parts were blended to prepare a resin composition. The storage stability of the obtained resin composition was good. This resin composition was diluted (solvent: xylene, solid content: 60%), and this was applied to a water plate with a bar coater and then treated at 140 ° C. for 30 minutes, but the resin did not cure and a coating film could not be obtained. It was
【００２６】比較例２ メチルナジック酸ジメチルエステル２２部に、エポキシ
樹脂（東都化成（株）製、エポトートＹＤ−１２８）１
９部、臭化テトラブチルアンモニウム０．８２部を配合
して樹脂組成物を調製した。得られた樹脂組成物の貯蔵
安定性は良好であった。この樹脂組成物を希釈（溶剤：
キシレン、固形分：６０％）し、これをバーコータで水
研板に塗布した後１４０℃で３０分間処理したが樹脂が
硬化せず塗膜が得られなかった。Comparative Example 2 22 parts of methyl naphthic acid dimethyl ester was mixed with 1 part of an epoxy resin (Epototo YD-128 manufactured by Tohto Kasei Co., Ltd.).
9 parts and tetrabutylammonium bromide 0.82 parts were blended to prepare a resin composition. The storage stability of the obtained resin composition was good. Dilute this resin composition (solvent:
Xylene, solid content: 60%) was applied to a water-inspecting plate with a bar coater and then treated at 140 ° C. for 30 minutes, but the resin was not cured and a coating film could not be obtained.
【００２７】比較例３ 無水メチルナジック酸１７部に、エポキシ樹脂（東都化
成（株）製、エポトートＹＤ−１２８）１９部、臭化テ
トラブチルアンモニウム０．７２部を配合して樹脂組成
物を調製した。得られた樹脂組成物の貯蔵安定性は不良
であった。この樹脂組成物を希釈（溶剤：キシレン、固
形分：６０％）し、これをバーコーターで水研板に塗布
した後、１４０℃で３０分間焼き付けた。得られた塗膜
の鉛筆硬度はＨであった。Comparative Example 3 A resin composition was prepared by mixing 17 parts of methyl nadic acid anhydride with 19 parts of an epoxy resin (Epototo YD-128 manufactured by Tohto Kasei Co., Ltd.) and 0.72 part of tetrabutylammonium bromide. did. The storage stability of the obtained resin composition was poor. This resin composition was diluted (solvent: xylene, solid content: 60%), applied to a water-inspecting plate with a bar coater, and then baked at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was H.
【００２８】[0028]
【発明の効果】本発明の、（メチル）ナジック酸ハーフ
エステルは、加熱により容易に酸無水物を形成すること
ができるものであり、熱硬化性樹脂用架橋剤として用い
ると、貯蔵安定性に優れ、組成成分全体を一液化するこ
とが可能となり、工業上非常に有益なものである。INDUSTRIAL APPLICABILITY The (methyl) naphthic acid half ester of the present invention is capable of easily forming an acid anhydride by heating, and when used as a crosslinking agent for thermosetting resin, it has excellent storage stability. It is excellent and it is possible to liquefy all the composition components, which is very useful in industry.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩本 暁生 愛知県名古屋市東区砂田橋四丁目１番60号 三菱レイヨン株式会社商品開発研究所内 (72)発明者 岩瀬 国男 愛知県名古屋市東区砂田橋四丁目１番60号 三菱レイヨン株式会社商品開発研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Iwamoto 4-chome, Sunadabashi, Higashi-ku, Aichi Prefecture, Aichi Prefecture 60-62, Product Development Laboratory, Mitsubishi Rayon Co., Ltd. No. 60 Mitsubishi Rayon Co., Ltd. Product Development Laboratory
Claims (2)
とする（メチル）ナジック酸ハーフエステル。 【化１】 （式中、Ｒは水素またはメチル基であり、ｎは１〜４の
整数である。）1. A (methyl) naphthic acid half ester having a structure represented by the general formula (1). [Chemical 1] (In the formula, R is hydrogen or a methyl group, and n is an integer of 1 to 4.)
フエステルからなる熱硬化性樹脂用架橋剤。2. A cross-linking agent for a thermosetting resin, which comprises the (methyl) naphthic acid half ester according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31658993A JP3782469B2 (en) | 1993-11-12 | 1993-12-16 | Thermosetting resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-283535 | 1993-11-12 | ||
| JP28353593 | 1993-11-12 | ||
| JP31658993A JP3782469B2 (en) | 1993-11-12 | 1993-12-16 | Thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07179399A true JPH07179399A (en) | 1995-07-18 |
| JP3782469B2 JP3782469B2 (en) | 2006-06-07 |
Family
ID=17666795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31658993A Expired - Lifetime JP3782469B2 (en) | 1993-11-12 | 1993-12-16 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3782469B2 (en) |
-
1993
- 1993-12-16 JP JP31658993A patent/JP3782469B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3782469B2 (en) | 2006-06-07 |
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