JPH07188114A - (methyl)tetrahydrophthalic acid half ester and crosslinking agent - Google Patents
(methyl)tetrahydrophthalic acid half ester and crosslinking agentInfo
- Publication number
- JPH07188114A JPH07188114A JP32885893A JP32885893A JPH07188114A JP H07188114 A JPH07188114 A JP H07188114A JP 32885893 A JP32885893 A JP 32885893A JP 32885893 A JP32885893 A JP 32885893A JP H07188114 A JPH07188114 A JP H07188114A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- half ester
- formula
- acid half
- anhydride
- 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
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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)テトラヒドロフタル酸
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) tetrahydrophthalic acid half ester which is the first invention of the present invention is represented by the following general formula (1).
【0006】[0006]
【化2】 (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)テトラヒド
ロフタル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)テトラヒド
ロフタル酸は、テトラヒドロフタル酸あるいはメチルテ
トラヒドロフタル酸を示す。[Chemical 2] (In the formula, R is hydrogen or a methyl group, and n is an integer of 1 to 4.) The cross-linking agent for thermosetting resin, which is the second invention of the present invention, has the above general formula (1). (Methyl) tetrahydrophthalic acid half ester represented by In the present invention, (methyl) tetrahydrophthalic acid means tetrahydrophthalic acid or methyltetrahydrophthalic acid.
【0007】本発明の(メチル)テトラヒドロフタル酸
ハーフエステルは、無水(メチル)テトラヒドロフタル
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)テトラヒドロフタル酸
ハーフエステルの酸無水物への変化率著しく低下するた
めである。The (methyl) tetrahydrophthalic acid half ester of the present invention can be synthesized by reacting (methyl) tetrahydrophthalic anhydride with monohydric alcohols 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, it is important that the monohydric alcohols have 1 to 4 carbon atoms, that is, n in the general formula (1) is 1 to 4. This is because when the monohydric alcohol has 5 or more carbon atoms, the rate of change of the obtained (methyl) tetrahydrophthalic acid half ester to an acid anhydride is significantly reduced.
【0008】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)テトラヒドロフタル酸:一価アルコール類=1:
1〜1:20の範囲であり、好ましくは1:2〜1:5
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)テトラヒドロフタル酸に対して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4
0〜100℃、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, for example, amines such as triethylamine, tributylamine and dimethylaniline are suitable. The molar ratio of the reactants is (methyl) tetrahydrophthalic anhydride: monohydric alcohols = 1:
It is in the range of 1 to 1:20, preferably 1: 2 to 1: 5.
Is. When a basic catalyst is used, its addition amount is 0.1 to relative to (methyl) tetrahydrophthalic anhydride.
200 mole percent, preferably 1-100 mole percent. The reaction temperature is 4 in the case of no catalyst.
0 to 100 ° C, preferably 60 to 80 ° C, and 0 to 80 ° C, preferably 20 to 80 ° C when a basic catalyst is used.
It is 50 ° C.
【0009】このようにして得られた本発明の(メチ
ル)テトラヒドロフタル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)テトラヒドロフタル酸
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 (methyl) tetrahydrophthalic acid half ester of the present invention thus obtained 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) tetrahydrophthalic acid half ester of the present invention has the above-mentioned characteristics, and when used as a cross-linking agent for a thermosetting resin typified by an epoxy group-containing resin or the like, it has extremely good storage stability. Therefore, it is possible to make the whole of these compositions into one liquid, and it is particularly effective as a crosslinking agent for thermosetting resins used in paints, adhesives and the like.
【0010】本発明の(メチル)テトラヒドロフタル酸
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) tetrahydrophthalic acid half ester of the present invention is used as a crosslinking agent for thermosetting resins, the rate of conversion to 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.
【0011】[0011]
【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. ).
【0012】・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 the "pencil scratch test" of JIS K-5400. 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.
【0013】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、無水メチルテトラヒドロフタル酸
(新日本理化(株)製、リカシッドMT)166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、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、無色透明液体のメチルテトラヒドロフタル酸モ
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85%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 166 parts of methyltetrahydrophthalic anhydride (Rikaacid MT manufactured by Shin Nippon Rika Co., Ltd.) and 160 parts of methanol. The mixture was reacted at 70 ° C for 6 hours. By infrared absorption spectrum measurement, after confirming that the absorption characteristics of the acid anhydride group (1780 cm -1 , 1860 cm -1 ) have disappeared and the absorption characteristics of the carboxyl group (2400-3400 cm -1 ) have occurred, Excessive methanol was distilled off under reduced pressure to obtain methyl tetrahydrophthalic acid monomethyl ester (H-1) as a colorless transparent liquid. The rate of conversion of the obtained half ester to an acid anhydride was 85%.
【0014】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、無水テトラヒドロフタル酸(新日本
理化(株)製、リカシッドTH)152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(1780
cm-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、白
色結晶のテトラヒドロフタル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85%であった。Production Example 2 A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a temperature controller was charged with 152 parts of tetrahydrophthalic anhydride (Rikacid TH, manufactured by Shin Nippon Rika Co., Ltd.) and 160 parts of methanol, The reaction was carried out at 70 ° C for 6 hours. Infrared absorption spectrum measurement showed that the absorption characteristics of the acid anhydride group (1780
cm -1, 1860 cm -1) disappeared, after the absorption characteristics of the carboxyl group (2400~3400cm -1) it was confirmed that has occurred, then evaporated under reduced pressure and excess methanol, tetrahydrophthalic acid as white crystals Monomethyl ester (H
-2) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 85%.
【0015】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、無水メチルテトラヒドロフタル酸
(新日本理化(株)製、リカシッドMT)166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(1780cm-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
ールを減圧留去し、無色透明液体のメチルテトラヒドロ
フタル酸モノヘキシルエステル(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10%以下
であった。Production Example 3 In a four-necked flask equipped with a thermometer, a stirrer, a condenser and a temperature controller, 166 parts of methyl tetrahydrophthalic anhydride (Rikacide MT, manufactured by Shin Nippon Rika Co., Ltd.)
-Hexanol 153 parts was charged and reacted at 70 ° C for 6 hours. Infrared absorption spectrum measurement revealed that the absorption characteristics of the acid anhydride group (1780 cm -1 , 1860 cm -1 ) disappeared and the absorption characteristics of the carboxyl group (2400-3400 cm -1 )
Was confirmed, the excess n-hexanol was distilled off under reduced pressure to obtain a colorless transparent liquid of methyltetrahydrophthalic acid monohexyl ester (H-3). The rate of conversion of the obtained half ester to an acid anhydride was 10% or less.
【0016】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、無水テトラヒドロフタル酸(新日本
理化(株)製、リカシッドTH)152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(1
780cm-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−ヘキサノールを減
圧留去し、無色透明液体のテトラヒドロフタル酸モノヘ
キシルエステル(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10%以下であった。Production Example 4 In a four-necked flask equipped with a thermometer, a stirrer, a condenser and a temperature controller, 152 parts of tetrahydrophthalic anhydride (Rikacid TH, manufactured by Shin Nippon Rika Co., Ltd.) and 153 parts of n-hexanol were placed. After charging, the mixture was reacted at 70 ° C. for 6 hours.
The absorption characteristics of the acid anhydride group (1
780 cm −1 , 1860 cm −1 ) disappeared, and after confirming that the absorption characteristics of the carboxyl group (2400 to 3400 cm −1 ) have occurred, excess n-hexanol was distilled off under reduced pressure to obtain a colorless transparent liquid. Tetrahydrophthalic acid monohexyl ester (H-4) was obtained. The rate of conversion of the obtained half ester to an acid anhydride was 10% or less.
【0017】実施例1 メチルテトラヒドロフタル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−128)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 Methyl tetrahydrophthalic acid monomethyl ester (H-
1) 20 parts were mixed with 19 parts of an epoxy resin (manufactured by Tohto Kasei Co., Ltd., Epotote YD-128) and 0.78 part of tetrabutylammonium bromide to prepare a resin composition. The storage stability of the obtained resin composition was good. Dilute this resin composition (solvent: xylene, solid content: 60%)
Then, after applying this to a water plate with a bar coater,
Baked at 30 ° C for 30 minutes. The pencil hardness of the obtained coating film is H
Met.
【0018】実施例2 テトラヒドロフタル酸モノメチルエステル(H−2)1
8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
0.76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 Tetrahydrophthalic acid monomethyl ester (H-2) 1
A resin composition was prepared by mixing 8 parts with 19 parts of an epoxy resin (Epototo YD-128 manufactured by Tohto Kasei Co., Ltd.) and 0.76 part of tetrabutylammonium bromide. 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 H.
【0019】比較例1 メチルテトラヒドロフタル酸モノヘキシルエステル(H
−3)28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0.94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 Methyltetrahydrophthalic acid monohexyl ester (H
-3) To 28 parts, 19 parts of an epoxy resin (Epototo YD-128 manufactured by Tohto Kasei Co., Ltd.) and 0.94 part of tetrabutylammonium bromide were mixed to prepare a resin composition.
The storage stability of the obtained resin composition was good. Dilute this resin composition (solvent: xylene, solid content: 60%)
Then, after coating this on a water plate with a bar coater, 140 ° C
However, the resin was not cured and a coating film could not be obtained.
【0020】比較例2 テトラヒドロフタル酸モノヘキシルエステル(H−4)
27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0.92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 Tetrahydrophthalic acid monohexyl ester (H-4)
A resin composition was prepared by mixing 27 parts with 19 parts of an epoxy resin (Epototo YD-128 manufactured by Tohto Kasei Co., Ltd.) and 0.92 part of tetrabutylammonium bromide. 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 treated at 140 ° C. for 30 minutes, but the resin did not cure and a coating film could not be obtained. .
【0021】比較例3 無水メチルテトラヒドロフタル酸16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0.7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分間処理した。得られた
塗膜の鉛筆硬度はHであった。Comparative Example 3 Methyltetrahydrophthalic anhydride (16 parts) was mixed with an epoxy resin (Epototo YD-128, manufactured by Tohto Kasei Co., Ltd.) 19
Part, and 0.7 part of tetrabutylammonium bromide were mixed to prepare a resin composition. 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 treated at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was H.
【0022】比較例4 無水テトラヒドロフタル酸18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0.74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分間処理した。得られた塗
膜の鉛筆硬度はHであった。Comparative Example 4 A resin composition was prepared by mixing 18 parts of tetrahydrophthalic anhydride with 19 parts of an epoxy resin (Epototo YD-128 manufactured by Tohto Kasei Co., Ltd.) and 0.74 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 treated at 140 ° C. for 30 minutes. The pencil hardness of the obtained coating film was H.
【0023】[0023]
【発明の効果】本発明の、(メチル)テトラヒドロフタ
ル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) tetrahydrophthalic 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 storage stability. It is excellent, and it is possible to liquefy all the composition components, which is very useful industrially.
───────────────────────────────────────────────────── 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 (72)発明者 藤江 忍 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 (72) Inventor Shinobu Fujie 4-60 Sunadabashi, Higashi-ku, Nagoya, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Laboratory
Claims (2)
とする(メチル)テトラヒドロフタル酸ハーフエステ
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) tetrahydrophthalic 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.)
タル酸ハー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) tetrahydrophthalic acid half ester according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32885893A JP3782470B2 (en) | 1993-12-24 | 1993-12-24 | Thermosetting resin composition |
Applications Claiming Priority (1)
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JP32885893A JP3782470B2 (en) | 1993-12-24 | 1993-12-24 | Thermosetting resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07188114A true JPH07188114A (en) | 1995-07-25 |
JP3782470B2 JP3782470B2 (en) | 2006-06-07 |
Family
ID=18214885
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JP32885893A Expired - Lifetime JP3782470B2 (en) | 1993-12-24 | 1993-12-24 | Thermosetting resin composition |
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JP (1) | JP3782470B2 (en) |
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1993
- 1993-12-24 JP JP32885893A patent/JP3782470B2/en not_active Expired - Lifetime
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