JPH0559148A - Production of acid-modified epoxy resin - Google Patents
Production of acid-modified epoxy resinInfo
- Publication number
- JPH0559148A JPH0559148A JP22075291A JP22075291A JPH0559148A JP H0559148 A JPH0559148 A JP H0559148A JP 22075291 A JP22075291 A JP 22075291A JP 22075291 A JP22075291 A JP 22075291A JP H0559148 A JPH0559148 A JP H0559148A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- epoxy resin
- fatty acid
- polyhydroxy compound
- hydroxyl group
- 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
Landscapes
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸変性エポキシ樹脂の
製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing an acid-modified epoxy resin.
【０００２】[0002]
【従来の技術】不飽和脂肪酸変性エポキシ樹脂は、可撓
性や耐レトルト性に優れるため、金属特に製缶塗料用樹
脂として多用されている。2. Description of the Related Art Unsaturated fatty acid-modified epoxy resins are widely used as resins for metals, especially can coatings, because of their excellent flexibility and retort resistance.
【０００３】従来の不飽和脂肪酸変性エポキシ樹脂は、
例えば、分子中に第２級水酸基を有するビスフェノー
ルＡポリグリシジルエーテルと不飽和脂肪酸とを反応さ
せたり、特開昭６２−１１２６６４号公報に記載され
ているように、分子中に第２級水酸基を有するビスフェ
ノールＡジグリシジルエーテルと不飽和脂肪酸アルコー
ルエステルとをエステル交換反応させることにより製造
されていた。Conventional unsaturated fatty acid-modified epoxy resins are
For example, a bisphenol A polyglycidyl ether having a secondary hydroxyl group in the molecule is reacted with an unsaturated fatty acid, or a secondary hydroxyl group is introduced into the molecule as described in JP-A-62-112664. It was produced by transesterifying the bisphenol A diglycidyl ether that it has with an unsaturated fatty acid alcohol ester.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記
の方法で得られた不飽和脂肪酸変性エポキシ樹脂は硬化
性が乏しくなり、そのため塗料として用いた場合に塗膜
の乾燥性が悪く、流れ作業的な塗装作業工程において、
塗装された金属板を重ねておいた場合に金属板同士が密
着し剥離できなくなる所謂ブロッキングの問題を起こし
易く、また、塗膜硬性が低いために塗膜に傷が付き易い
等の問題点を有していた。次に上記の方法で得られた
不飽和脂肪酸変性エポキシ樹脂は、塗膜の硬化性が高い
ための方法で得られた不飽和脂肪酸変性エポキシ樹脂
の問題点を解決できるものであるが、未反応の不飽和脂
肪酸アルコールエステルが多量に残留するために、塗膜
の耐溶剤性や耐レトルト性が悪く、更に熱硬化性塗料と
して用いると、乾燥硬化時に有害な不飽和脂肪酸アルコ
ールエステルが蒸散するという欠点もあった。However, the unsaturated fatty acid-modified epoxy resin obtained by the above-mentioned method has poor curability, so that when used as a paint, the drying property of the coating film is poor and the workability is low. In the painting process
When coated metal plates are piled up, it is easy to cause so-called blocking problem that metal plates adhere to each other and cannot be peeled off, and the coating film hardness is low, so that the coating film is easily scratched. Had. Next, the unsaturated fatty acid-modified epoxy resin obtained by the above method can solve the problems of the unsaturated fatty acid-modified epoxy resin obtained by the method due to the high curability of the coating film. Since a large amount of unsaturated fatty acid alcohol ester remains, the solvent resistance and retort resistance of the coating film are poor, and when it is used as a thermosetting paint, harmful unsaturated fatty acid alcohol ester is evaporated during dry curing. There were also drawbacks.
【０００５】本発明が解決しようとする課題は、塗料と
して使用した場合にブロッキングを起こす事がなく、ま
た不飽和脂肪酸及び不飽和脂肪酸アルコールエステル等
の有害物質の残留を著しく低く押さえることによって、
塗膜の耐溶剤性や耐レトルト性の向上及び塗膜硬化時の
有害物質の蒸散防止を実現した酸変性エポキシ樹脂の製
造方法を提供することにある。The problem to be solved by the present invention is that it does not cause blocking when used as a paint, and it keeps the residual amount of harmful substances such as unsaturated fatty acids and unsaturated fatty acid alcohol esters to be extremely low.
It is an object of the present invention to provide a method for producing an acid-modified epoxy resin that realizes improvement in solvent resistance and retort resistance of a coating film and prevention of evaporation of harmful substances when the coating film is cured.
【０００６】[0006]
【課題を解決するための手段】そこで本発明者らは、ブ
ロッキングを起こす事がなく、しかも有害物質である原
料物質の不飽和脂肪酸の残留が極めて少ないエポキシ基
を少なくとも２個含有する酸変性エポキシ樹脂を得るべ
く鋭意検討したところ、第２級水酸基を有しかつフェノ
ール性水酸基を少なくとも２個含有するポリヒドロキシ
化合物の第２級水酸基を不飽和脂肪酸のカルボキシル基
と反応させた後、これをエポキシ化するという方法で得
られた酸変性エポキシ樹脂が上記の特徴を有しているこ
とを見い出し、本発明を完成するに至った。Therefore, the present inventors have found that an acid-modified epoxy containing at least two epoxy groups which does not cause blocking and has very little residual unsaturated fatty acid as a raw material which is a harmful substance. As a result of diligent studies to obtain a resin, the secondary hydroxyl group of a polyhydroxy compound having a secondary hydroxyl group and containing at least two phenolic hydroxyl groups was reacted with a carboxyl group of an unsaturated fatty acid, and then an epoxy resin was prepared. It was found that the acid-modified epoxy resin obtained by the method of converting the compound has the above-mentioned characteristics, and completed the present invention.
【０００７】即ち本発明は、第２級水酸基を有しかつフ
ェノール性水酸基を少なくとも２個含有するポリヒドロ
キシ化合物（Ａ）の第２級水酸基とモノカルボン酸
（Ｂ）とを反応せしめた酸変性化合物を得る第１工程、
次いでエポキシ化してエポキシ樹脂を得る第２工程、か
らなることを特徴とする酸変性エポキシ樹脂の製造方法
に関する。That is, the present invention is an acid modification in which a secondary hydroxyl group of a polyhydroxy compound (A) having a secondary hydroxyl group and containing at least two phenolic hydroxyl groups is reacted with a monocarboxylic acid (B). A first step of obtaining a compound,
Next, the present invention relates to a method for producing an acid-modified epoxy resin, which comprises a second step of epoxidizing to obtain an epoxy resin.
【０００８】本発明に係わる第２級水酸基を有しかつフ
ェノール性水酸基を少なくとも２個含有するポリヒドロ
キシ化合物（Ａ）としては、例えば −ＣＨ2ＣＨ（Ｏ
Ｈ）ＣＨ2−結合または −ＣＨ2Ｃ（ＣＨ3）（ＯＨ）Ｃ
Ｈ2−結合とビスフェノール骨格の繰り返し単位からな
るものが挙げられ、具体的にはビスフェノールジグリシ
ジルエーテル型エポキシ樹脂をビスフェノール過剰の条
件下で、重合せしめたものが挙げられる。ここで用いる
ビスフェノールとしては例えば、ビスフェノールＡ、ビ
スフェノールＦ、ビスフェノールＡＦ、ビスフェノール
Ｓ等が挙げられ、また重合せしめたビスフェノールジグ
リシジルエーテル型エポキシ樹脂としては、例えばビス
フェノールＡジグリシジルエーテル型エポキシ樹脂、ビ
スフェノールＦジグリシジルエーテル型エポキシ樹脂、
ビスフェノールＡＦジグリシジルエーテル型エポキシ樹
脂、ビスフェノールＳジグリシジルエーテル型エポキシ
樹脂等が挙げられるが、中でも下記構造式１及び下記構
造式２で表わされるポリヒドロキシ化合物が好ましく使
用できる。構造式１The polyhydroxy compound (A) having a secondary hydroxyl group and containing at least two phenolic hydroxyl groups according to the present invention is, for example, --CH 2 CH (O
H) CH 2 - bond or -CH 2 C (CH 3) ( OH) C
Examples thereof include those having a repeating unit of H 2 -bond and bisphenol skeleton, and specific examples thereof include those obtained by polymerizing a bisphenol diglycidyl ether type epoxy resin under an excess of bisphenol. Examples of the bisphenol used here include bisphenol A, bisphenol F, bisphenol AF, and bisphenol S. Examples of the polymerized bisphenol diglycidyl ether type epoxy resin include bisphenol A diglycidyl ether type epoxy resin and bisphenol F. Diglycidyl ether type epoxy resin,
Examples thereof include bisphenol AF diglycidyl ether type epoxy resin and bisphenol S diglycidyl ether type epoxy resin. Among them, polyhydroxy compounds represented by the following structural formulas 1 and 2 can be preferably used. Structural formula 1
【０００９】[0009]
【化１】 [Chemical 1]
【００１０】構造式１において、ｎは１以上である。 構造式２In Structural Formula 1, n is 1 or more. Structural formula 2
【００１１】[0011]
【化２】 [Chemical 2]
【００１２】構造式２において、ｎは１以上である。ビ
スフェノールポリグリシジルエーテル型エポキシ樹脂と
ビスフェノールとの重合反応の条件は特に限定されるも
のではないが、通常８０〜１８０℃で３０分〜６時間で
ある。又、この反応の際には通常触媒が使用できる。触
媒としては、例えば水酸化ナトリウム、水酸化カリウ
ム、炭酸ナトリウム、塩化アンモニウム等が挙げられ
る。In Structural Formula 2, n is 1 or more. The conditions for the polymerization reaction of the bisphenol polyglycidyl ether type epoxy resin and bisphenol are not particularly limited, but are usually 80 to 180 ° C. and 30 minutes to 6 hours. Further, a catalyst can be usually used in this reaction. Examples of the catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium chloride and the like.
【００１３】上記重合反応の際には必要に応じて、有機
溶剤を用いてもよい。有機溶剤としては、例えばトルエ
ン、キシレン、メシチレン、プソイドキュメン、エクソ
ン化学社製有機溶剤「ソルベッソ」等が挙げられる。In the above polymerization reaction, an organic solvent may be used if necessary. Examples of the organic solvent include toluene, xylene, mesitylene, pseudocumene, and an organic solvent “Solvesso” manufactured by Exxon Chemical Company.
【００１４】上記した様にして得られるポリヒドロキシ
化合物（Ａ）は、通常分子量７００〜８０００のもので
あり、中でも１０００〜３０００のものが好ましい。次
に第１工程として、このポリヒドロキシ化合物（Ａ）に
モノカルボン酸（Ｂ）を反応させ脱水縮合せしめて、ポ
リヒドロキシ化合物（Ａ）の第２級水酸基とモノカルボ
ン酸（Ｂ）のカルボキシル基をエステル結合させる。こ
の際に用いられるモノカルボン酸（Ｂ）としては、公知
慣用のものがいずれも使用できる。具体的には、例え
ば、ギ酸、酢酸、プロピオン酸、酪酸等の飽和脂肪族モ
ノカルボン酸、リノール酸、リノレン酸、エレオステア
リン酸、リカン酸、脱水ヒマシ油脂肪酸、アマニ油脂肪
酸、桐油脂肪酸、オイジチカ油脂肪酸、大豆油脂肪酸、
サフラワー油脂肪酸、ヒマワリ油脂肪酸、トール油脂肪
酸等の不飽和脂肪酸が挙げられる。モノカルボン酸
（Ｂ）としては、エポキシ樹脂を塗料として使用した際
に、塗工時の塗膜の酸化重合が促進される点から、特に
脱水ヒマシ油脂肪酸、アマニ油脂肪酸、桐油脂肪酸、オ
イジチカ油脂肪酸、大豆油脂肪酸、サフラワー油脂肪
酸、ヒマワリ油脂肪酸、トール油脂肪酸等の要素価１２
０以上の不飽和脂肪酸が好ましい。The polyhydroxy compound (A) obtained as described above usually has a molecular weight of 700 to 8000, and preferably 1000 to 3000. Next, as a first step, the polyhydroxy compound (A) is reacted with a monocarboxylic acid (B) for dehydration condensation to give a secondary hydroxyl group of the polyhydroxy compound (A) and a carboxyl group of the monocarboxylic acid (B). Is ester-bonded. As the monocarboxylic acid (B) used at this time, any known and conventional one can be used. Specifically, for example, formic acid, acetic acid, propionic acid, saturated aliphatic monocarboxylic acids such as butyric acid, linoleic acid, linolenic acid, eleostearic acid, licanoic acid, dehydrated castor oil fatty acid, linseed oil fatty acid, tung oil fatty acid, Oedichka oil fatty acid, soybean oil fatty acid,
Unsaturated fatty acids such as safflower oil fatty acid, sunflower oil fatty acid, tall oil fatty acid and the like can be mentioned. Examples of the monocarboxylic acid (B) include dehydrated castor oil fatty acid, linseed oil fatty acid, tung oil fatty acid, and oijika oil, since oxidative polymerization of the coating film is promoted when the epoxy resin is used as a paint. Element value 12 such as fatty acid, soybean oil fatty acid, safflower oil fatty acid, sunflower oil fatty acid, tall oil fatty acid
Unsaturated fatty acids of 0 or more are preferred.
【００１５】ポリヒドロキシ化合物（Ａ）とモノカルボ
ン酸（Ｂ）の脱水縮合反応の条件は特に限定されるもの
ではないが、通常１５０〜２５０℃で１時間〜８時間で
あって、その配合比率は重量比で（Ａ）／（Ｂ）＝１．
０／０．１〜１．０／０．８好ましくは（Ａ）／（Ｂ）
＝１．０／０．４〜１．０／０．７である。The conditions for the dehydration condensation reaction of the polyhydroxy compound (A) and the monocarboxylic acid (B) are not particularly limited, but they are usually at 150 to 250 ° C. for 1 to 8 hours, and the mixing ratio thereof. Is a weight ratio of (A) / (B) = 1.
0 / 0.1 to 1.0 / 0.8 preferably (A) / (B)
= 1.0 / 0.4 to 1.0 / 0.7.
【００１６】脱水縮合反応を行うに際しては、必要に応
じて、公知慣用の触媒、例えばテトライソプロピルチタ
ネート、オクチル酸ジルコニウム等を使用することもで
きる。In carrying out the dehydration condensation reaction, known and conventional catalysts such as tetraisopropyl titanate and zirconium octylate may be used, if necessary.
【００１７】この第１工程である脱水縮合反応では、モ
ノカルボン酸（Ｂ）は、モノカルボン酸そのもの使用す
るが、モノカルボン酸のアルコールエステルを用いてエ
ステル交換反応を行うことも出来る。しかしその場合に
は、不飽和脂肪酸アルコールエステル等の有害物質の残
留を著しく低く押さえることができる、という本発明の
特徴を欠いたエポキシ樹脂しか得られないことになる。In the dehydration condensation reaction which is the first step, the monocarboxylic acid (B) is used as the monocarboxylic acid itself, but the transesterification reaction can also be carried out using an alcohol ester of the monocarboxylic acid. However, in that case, only an epoxy resin lacking the feature of the present invention that the residue of harmful substances such as unsaturated fatty acid alcohol ester can be suppressed to a very low level can be obtained.
【００１８】次いで、第２工程として、このポリヒドロ
キシ化合物にエポキシ基供給物質（Ｃ）を反応せしめる
ことにより本発明に係わるエポキシ樹脂は製造される。
エポキシ基供給物質（Ｃ）は公知慣用のものがいずれも
使用できるが、例えば上記ポリヒドロキシ化合物（Ａ）
を製造する際に用いることができるビスフェノールジグ
リシジルエーテル型エポキシ樹脂の他に、ジヒドロキシ
ナフタレンジグリシジルエーテル型エポキシ樹脂や、フ
ェノールノボラック樹脂ポリグリシジルエーテル型エポ
キシ樹脂、クレゾールノボラック樹脂ポリグリシジルエ
ーテル型エポキシ樹脂等のノボラック樹脂ポリグリシジ
ルエーテル型エポキシ樹脂、ポリアルキレングリコール
と脂肪族ジカルボン酸とのポリエステルのジグリシジル
エステル型エポキシ樹脂、脂肪族ジオールと脂肪族ジカ
ルボン酸とのポリエステルのジグリシジルエステル型エ
ポキシ樹脂等のポリエステルジグリシジルエステル型エ
ポキシ樹脂、下記構造式３で表わされるジフェニルメタ
ンジアミンテトラグリシジル等のジアミンテトラグリシ
ジル型エポキシ樹脂等が挙げられる。 構造式３Then, as a second step, the epoxy resin according to the present invention is produced by reacting the polyhydroxy compound with an epoxy group supplying substance (C).
As the epoxy group-providing substance (C), any known and commonly used one can be used. For example, the above-mentioned polyhydroxy compound (A)
In addition to bisphenol diglycidyl ether type epoxy resin that can be used in the production of, dihydroxynaphthalene diglycidyl ether type epoxy resin, phenol novolac resin polyglycidyl ether type epoxy resin, cresol novolac resin polyglycidyl ether type epoxy resin, etc. Novolak resin Polyglycidyl ether type epoxy resin, polyester of diglycidyl ester type epoxy resin of polyester of polyalkylene glycol and aliphatic dicarboxylic acid, polyester of diglycidyl ester type epoxy resin of polyester of aliphatic diol and aliphatic dicarboxylic acid, etc. Diglycidyl ester type epoxy resin, diphenylmethanediamine tetraglycidyl diamine tetraglycidyl type epoxy resin represented by the following structural formula 3 Etc. The. Structural formula 3
【００１９】[0019]
【化３】 [Chemical 3]
【００２０】エポキシ基供給物質（Ｃ）は、それを選択
することにより、最終的に硬化した際の塗膜にあらゆる
特徴を付与することが可能である。例えば、エポキシ基
供給物質（Ｃ）としてノボラック樹脂ポリグリシジルエ
ーテル型エポキシ樹脂を用いて得たエポキシ樹脂を塗料
として用いた場合、その硬化塗膜は、より耐溶剤性や、
耐ブロックキング性が向上するという傾向があるし、ポ
リエステルのジグルシジルエステル型エポキシ樹脂を用
いて得たエポキシ樹脂を塗料として用いた場合、その硬
化塗膜は、可撓性に優れたものとなる傾向がある。By selecting the epoxy group-providing substance (C), it is possible to impart all characteristics to the coating film when it is finally cured. For example, when an epoxy resin obtained by using a novolac resin polyglycidyl ether type epoxy resin as the epoxy group supplying substance (C) is used as a paint, the cured coating film has more solvent resistance and
Blocking resistance tends to be improved, and when an epoxy resin obtained by using a polyester diglycidyl ester type epoxy resin is used as a coating material, the cured coating film has excellent flexibility. Tend.
【００２１】本発明における第２工程の反応条件、即ち
第２級水酸基とモノカルボン酸が縮合した構造を有しか
つフェノール性水酸基を少なくとも２個含有する酸変性
化合物とエポキシ基供給物質との反応条件は特に制限さ
れるものではないが、通常１００〜２５０℃で１〜８時
間重合反応を行えばよく、また、その配合比はモル比で
酸変性化合物／（Ｃ）＝１．０／１．０〜１．０／２．
０、好ましくは１．０／１．０〜１．０／２．０であ
る。この際には必要に応じて上記した如き触媒を使用し
てもよい。The reaction condition of the second step in the present invention, that is, the reaction between an acid-modified compound having a structure in which a secondary hydroxyl group and a monocarboxylic acid are condensed and containing at least two phenolic hydroxyl groups, and an epoxy group-supplying substance The conditions are not particularly limited, but usually the polymerization reaction may be carried out at 100 to 250 ° C. for 1 to 8 hours, and the compounding ratio thereof is a molar ratio of acid-modified compound / (C) = 1.0 / 1. .0 to 1.0 / 2.
0, preferably 1.0 / 1.0 to 1.0 / 2.0. In this case, the catalyst as described above may be used if necessary.
【００２２】この様にして得られた酸変性エポキシ樹脂
は、塗料として用いた場合に耐ブロッキング性が著しく
向上し、しかもモノカルボン酸成分の含有量も全体の
０．５重量％以下と著しく少ないので有害なガスの発生
もほとんどないのである。The acid-modified epoxy resin thus obtained has significantly improved blocking resistance when used as a paint, and the content of the monocarboxylic acid component is significantly less than 0.5% by weight of the total. Therefore, there is almost no generation of harmful gas.
【００２３】この様にして得られた本発明の酸変性エポ
キシ樹脂は通常分子量８０００〜２００００のものであ
る。本発明の製造方法で得られた酸変性エポキシ樹脂
は、そのままで塗料、接着剤等各種用途に使用すること
ができる。例えば本発明で得られたエポキシ樹脂のう
ち、モノカルボン酸（Ｂ）として不飽和脂肪酸を用いた
ものは、分子内に重合性の不飽和二重結合を含有してい
るため、風乾により硬化させることができる。更にこの
風乾を促進するために金属ドライヤーを添加することが
できる。この際に使用できる金属ドライヤーは、特に制
限されないが、例えばナフテン酸コバルト、ナフテン酸
マンガン、ステアリン酸亜鉛、オクチル酸スズ、オクチ
ル酸コバルトマンガン等が挙げられる。本発明で得られ
たエポキシ樹脂には必要に応じて硬化剤、硬化促進剤、
充槙剤、有機溶剤、顔料、難燃剤、レベリング剤、可塑
剤、耐光安定剤、滑剤等の各種の添加剤を使用すること
ができる。The acid-modified epoxy resin of the present invention thus obtained usually has a molecular weight of 8,000 to 20,000. The acid-modified epoxy resin obtained by the production method of the present invention can be used as it is for various applications such as paints and adhesives. For example, among the epoxy resins obtained in the present invention, the one using unsaturated fatty acid as the monocarboxylic acid (B) contains a polymerizable unsaturated double bond in the molecule and therefore is cured by air drying. be able to. Further, a metal dryer can be added to accelerate the air drying. The metal dryer that can be used at this time is not particularly limited, and examples thereof include cobalt naphthenate, manganese naphthenate, zinc stearate, tin octylate, and cobalt manganese octylate. The epoxy resin obtained in the present invention, if necessary, a curing agent, a curing accelerator,
Various additives such as a filler, an organic solvent, a pigment, a flame retardant, a leveling agent, a plasticizer, a light resistance stabilizer, and a lubricant can be used.
【００２４】本発明の製造方法で得られた酸変性エポキ
シ樹脂を硬化するに当たって使用する事のできる硬化剤
としては、例えばブロックドポリイソシアネート、アミ
ノプラスト樹脂、フェノプラスト樹脂、ポリアミドポリ
アミン、マンニッヒ縮合物、低分子ポリアミン、ジシア
ンジアミド、リン酸等が挙げられるが、本発明の製造方
法で用いるエポキシ基供給物質（Ｃ）によっては、エポ
キシ基供給物質（Ｃ）との好ましい組み合わせが存在す
る。例えば、エポキシ基供給物質（Ｃ）としてノボラッ
クポリグリシジルエーテルを用いた時は、ブロックドポ
リイソシアネート、アミノプラスト樹脂が好適であり、
ビスフェノールポリグリシジルエーテルを用いた場合は
リン酸が好適である。The curing agent that can be used in curing the acid-modified epoxy resin obtained by the production method of the present invention is, for example, blocked polyisocyanate, aminoplast resin, phenoplast resin, polyamide polyamine, Mannich condensation product. , Low molecular weight polyamines, dicyandiamide, phosphoric acid, etc., but there are preferable combinations with the epoxy group-providing substance (C) depending on the epoxy group-providing substance (C) used in the production method of the present invention. For example, when novolac polyglycidyl ether is used as the epoxy group supplying substance (C), blocked polyisocyanate and aminoplast resin are suitable,
Phosphoric acid is preferred when bisphenol polyglycidyl ether is used.
【００２５】また、製缶用塗料として本発明で得られた
酸変性エポキシ樹脂を用いる場合には、硬化剤として燐
酸を用いることが好ましい。酸変性エポキシ樹脂と硬化
剤との混合比率は特に制限されるものではないが、通常
エポキシ樹脂のエポキシ基数と硬化剤の活性水素原子数
とを当量となる割合で用いる。硬化の条件は用いる硬化
剤の種類により異なるが、例えば硬化剤として燐酸を用
いる場合には１６０〜２５０℃で１〜１５分間加熱を行
えば良い。勿論、本発明で得られた酸変性エポキシ樹脂
が、モノカルボン酸（Ｂ）として不飽和脂肪酸を用いた
ものである場合には、更に金属ドライヤーを併用する事
もできる。When the acid-modified epoxy resin obtained in the present invention is used as a can-making coating material, phosphoric acid is preferably used as a curing agent. The mixing ratio of the acid-modified epoxy resin and the curing agent is not particularly limited, but usually the number of epoxy groups of the epoxy resin and the number of active hydrogen atoms of the curing agent are used in an equivalent ratio. The curing conditions vary depending on the type of curing agent used, but when phosphoric acid is used as the curing agent, heating may be performed at 160 to 250 ° C. for 1 to 15 minutes. Of course, when the acid-modified epoxy resin obtained in the present invention uses an unsaturated fatty acid as the monocarboxylic acid (B), a metal dryer can be further used in combination.
【００２６】本発明の製造方法で得られた酸変性エポキ
シ樹脂は各種金属加工品用塗料その他のビヒクルとして
好適に用いられているが、特に製缶用塗料の特にオーバ
ーコート用のクリヤー塗料として優れた塗膜硬度、可撓
性、保色性、耐レトルト性を示す。The acid-modified epoxy resin obtained by the production method of the present invention is preferably used as a paint for various metalwork products and other vehicles, but is particularly excellent as a clear paint for can coating, especially for overcoating. It exhibits coating film hardness, flexibility, color retention, and retort resistance.
【００２７】[0027]
【実施例】次に、本発明を実施例で詳しく説明する。以
下、特に断りのない限り「部」は「重量部」を「％」は
「重量％」を意味するものとする。EXAMPLES Next, the present invention will be described in detail with reference to Examples. Hereinafter, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.
【００２８】実施例１ 窒素導入管、温度計、デカンター、コンデンサー、攪拌
装置を具備した１リットルの四ツ口フラスコにソルベッ
ソ １５０（エクソン化学社製有機溶剤）５４．０部、
ＥＰＩＣＬＯＮ ８５０（大日本インキ化学工業社製ビ
スフェノールＡ型エポキシ樹脂、エポキシ当量１８８）
１１８．８部、ビスフェノールＡ９６．９部、５％水酸
化ナトリウム水溶液０．２２部を仕込み、１６０℃まで
昇温して１４０℃〜１６０℃を保持しながら４時間反応
し、分子量１０００のポリヒドロキシ化合物を得た。Example 1 54.0 parts of Solvesso 150 (organic solvent manufactured by Exxon Chemical Co.) was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a thermometer, a decanter, a condenser, and a stirrer.
EPICLON 850 (Bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188)
118.8 parts, bisphenol A 96.9 parts, 5% sodium hydroxide aqueous solution 0.22 parts were charged, and the temperature was raised to 160 ° C. and reacted for 4 hours while maintaining 140 ° C. to 160 ° C. The compound was obtained.
【００２９】次いでこのポリヒドロキシ化合物に脱水ヒ
マシ油脂肪酸１４２．８部、オクチル酸ジルコニウム１
２％（大日本インキ化学工業社製）０．８０部を添加
し、２２０℃まで昇温して同温度で６時間反応して固形
分酸価１以下の酸変性化合物を得た。（第１工程） 更に、ＥＰＩＣＬＯＮ ８５０の５０．８部、５％水酸
化ナトリウム水溶液０．４部を添加して１６０℃まで昇
温し同温度で３時間反応し、分子量９０００、エポキシ
当量７７０１の酸変性エポキシ樹脂１を得た。（第２工
程） この酸変性エポキシ樹脂１をソルベッソ １５０ １４
６．０部、ブチルセロソルブ ２００．０部、エチルセ
ロソルブ ２００．０部で希釈して不揮発分３９．７
％、粘度（ガードナー以下同じ）Ｔ−Ｕ、樹脂溶液の
（以下同じ）酸価０．２、樹脂溶液の（以下同じ）エポ
キシ当量１９４００の樹脂溶液を得た。Next, 142.8 parts of dehydrated castor oil fatty acid and 1 part of zirconium octylate were added to the polyhydroxy compound.
0.8% of 2% (manufactured by Dainippon Ink and Chemicals, Inc.) was added, the temperature was raised to 220 ° C., and the mixture was reacted at the same temperature for 6 hours to obtain an acid-modified compound having a solid content acid value of 1 or less. (First step) Furthermore, 50.8 parts of EPICLON 850 was added, and 0.4 part of a 5% aqueous sodium hydroxide solution was added, and the mixture was heated to 160 ° C. and reacted at the same temperature for 3 hours to give a molecular weight of 9000 and an epoxy equivalent of 7701. An acid-modified epoxy resin 1 was obtained. (Second step) This acid-modified epoxy resin 1 was dissolved in Solvesso 150 14
Non-volatile content 39.7 by diluting with 6.0 parts, butyl cellosolve 200.0 parts, ethyl cellosolve 200.0 parts.
%, Viscosity (Gardner and the same below) T-U, resin solution (the same below) acid value 0.2, and resin solution (the same below) epoxy equivalent 19400 resin solution was obtained.
【００３０】この樹脂溶液と燐酸を９９．８／０．２
（固形分比）で配合し、エチルセロソルブで希釈してク
リヤー塗料を調製した。 実施例２ 実施例１と同様の反応器で実施例１と同様に第１工程を
行った。This resin solution was mixed with phosphoric acid at 99.8 / 0.2.
(Solid content ratio), and diluted with ethyl cellosolve to prepare a clear coating. Example 2 The first step was carried out in the same manner as in Example 1 in the same reactor as in Example 1.
【００３１】更に、ＥＰＩＣＬＯＮ Ｎ−８６５（大日
本インキ化学工業社製ビスフェノールＡノボラック型エ
ポキシ樹脂、５〜６官能、エポキシ当量２１０）５０．
８部、５６％水酸化ナトリウム水溶液０．４部を添加し
て１６０℃まで昇温し同温度で３時間反応し、分子量１
２０００、エポキシ当量１１９００の酸変性エポキシ樹
脂２を得た。（第２工程） この酸変性エポキシ樹脂２をソルベッソ １５０ １４
６．０部、ブチルセロソルブ ２００．０部、エチルセ
ロソルブ ２００．０部で希釈して不揮発分４０．２
％、粘度Ｘ−Ｙ、酸価０．１、エポキシ当量２９８００
の樹脂溶液を得た。Further, EPICLON N-865 (bisphenol A novolac type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., 5 to 6 functional, epoxy equivalent 210) 50.
8 parts, 0.4 parts of a 56% sodium hydroxide aqueous solution were added, the temperature was raised to 160 ° C., and the mixture was reacted at the same temperature for 3 hours to give a molecular weight of 1
An acid-modified epoxy resin 2 having 2000 and an epoxy equivalent of 11900 was obtained. (Second step) This acid-modified epoxy resin 2 was applied to Solvesso 150 14
Diluted with 6.0 parts, butyl cellosolve 200.0 parts, ethyl cellosolve 200.0 parts to give a nonvolatile content of 40.2.
%, Viscosity XY, acid value 0.1, epoxy equivalent 29800
A resin solution of
【００３２】この樹脂溶液と燐酸を９９．８／０．２
（固形分比）で配合し、エチルセロソルブで希釈してク
リヤー塗料を調製した。 比較例１ 実施例１と同様の反応器にソルベッソ１５０の１２５．
０部、脱水ヒマシ油脂肪酸の１９５．３部を仕込み１６
０℃まで昇温した。１５０℃〜１６０℃を保持しながら
ＥＰＩＣＬＯＮ ４０５５（大日本インキ化学工業社製
ビスフェノール型エポキシ樹脂、エポキシ当量９６０）
の３１７．３部を徐々に添加した後、オクチル酸ジルコ
ニウム１２％ １．０部を添加して２２０℃まで昇温
し、同温度で４時間脱水縮合反応を行った。反応生成物
をソルベッソ１５０の７５．０部、ブチルセロソルブの
２００．０部、エチルセロソルブの１００．０部で希釈
して不揮発分４９．７％、粘度Ｕ、酸価０．２の樹脂溶
液を得た。This resin solution and phosphoric acid were added to 99.8 / 0.2
(Solid content ratio), and diluted with ethyl cellosolve to prepare a clear coating. Comparative Example 1 The same reactor as in Example 1 was used with 125.
Charged 0 part, dehydrated castor oil fatty acid 195.3 parts 16
The temperature was raised to 0 ° C. While maintaining 150 ° C to 160 ° C, EPICLON 4055 (Bisphenol type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 960)
Was gradually added, and then 1.0 part of 12% zirconium octylate was added, the temperature was raised to 220 ° C., and a dehydration condensation reaction was carried out at the same temperature for 4 hours. The reaction product was diluted with 75.0 parts of Solvesso 150, 200.0 parts of butyl cellosolve, and 100.0 parts of ethyl cellosolve to obtain a resin solution having a nonvolatile content of 49.7%, a viscosity U, and an acid value of 0.2. It was
【００３３】この樹脂溶液とリン酸を９９．８／０．２
（固形分比）で配合し、エチルセロソルブで希釈してク
リヤー塗料を調製した。 比較例２ 実施例１と同様の反応器にソルベッソ１５０の１００．
０部、脱水ヒマシ油脂肪酸メチルエステル（綜研化学社
製）の１２４．１部を仕込み１２０℃まで昇温した。１
１０℃〜１２０℃を保持しながらＥＰＩＣＬＯＮ ９０
５５（大日本インキ化学工業社製ビスフェノールＡ型エ
ポキシ樹脂、エポキシ当量２６００〜３０００）の２８
９．５部を徐々に添加した後、キャタリストＮ（大日本
インキ化学工業社製ナフテン酸リチウム）０．４部を添
加して２００℃まで昇温し、同温度で４時間メタノール
を溜去しながらエステル交換反応を行った。反応生成物
をソルベッソ １５０ １００．０部、ブチルセロソルブ
２００．０部、エチルセロソルブ ２００．０部で希釈
して不揮発分４０．５％、粘度Ｔ−Ｕ、酸価０．１、ポ
キシ当量１６６００の樹脂溶液を得た。This resin solution and phosphoric acid were added to 99.8 / 0.2
(Solid content ratio), and diluted with ethyl cellosolve to prepare a clear coating. Comparative Example 2 The same reactor as in Example 1 was used with 100.
04.1 parts and 124.1 parts of dehydrated castor oil fatty acid methyl ester (manufactured by Soken Chemical Industry Co., Ltd.) were charged and the temperature was raised to 120 ° C. 1
EPICLON 90 while maintaining 10 ° C to 120 ° C
28 of 55 (Bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 2600 to 3000)
After gradually adding 9.5 parts, 0.4 part of Catalyst N (lithium naphthenate manufactured by Dainippon Ink and Chemicals, Inc.) was added and the temperature was raised to 200 ° C., and methanol was distilled off at the same temperature for 4 hours. While carrying out the transesterification reaction. The reaction product was diluted with 100.0 parts of Solvesso 150, 200.0 parts of butyl cellosolve, and 200.0 parts of ethyl cellosolve to obtain a resin having a nonvolatile content of 40.5%, a viscosity TU, an acid value of 0.1, and a poxy equivalent of 16600. A solution was obtained.
【００３４】この樹脂溶液とリン酸を９９．８／０．２
（固形分比）で配合し、エチルセロソルブで希釈してク
リヤー塗料を調製した。上記実施例１〜２、比較例１〜
２で得た塗料を、ブリキ板に乾燥塗膜量として４５ｍｇ
／１００ｃｍ2 になるようバーコーターで塗布し、つい
で１８０℃１０分間加熱乾燥して試験片を作成した。This resin solution and phosphoric acid were mixed with 99.8 / 0.2
(Solid content ratio), and diluted with ethyl cellosolve to prepare a clear coating. Examples 1 and 2 and Comparative Example 1
The paint obtained in 2 was applied to a tin plate as a dry coating film amount of 45 mg.
/ 100 cm 2 was applied by a bar coater and then dried by heating at 180 ° C for 10 minutes to prepare a test piece.
【００３５】このようにして得られた試験片の塗膜性能
について、耐ブロッキング性、ガラス転移点、耐衝撃
性、耐屈曲性、耐レトルト性、保色性を調べ第１表に示
す結果を得た。また、加熱乾燥時の発煙性についても調
べ第１表に示す結果を得た。With respect to the coating film performance of the test piece thus obtained, the blocking resistance, glass transition point, impact resistance, flex resistance, retort resistance, and color retention were examined, and the results shown in Table 1 are shown. Obtained. Further, the smoke generation property during heating and drying was also examined, and the results shown in Table 1 were obtained.
【００３６】なお、各々の試験方法は次の通りである。 耐ブロッキング性 試験片を１３ｃｍ×１３ｃｍに切り、これを重ね合わせ
２ｋｇ／ｃｍ2 、５０℃で２時間加圧加温後、１２時間
加圧下に放冷して取り出し、試験片が相互に付着してい
るかどうか目視判定した。Each test method is as follows. Blocking resistance A test piece was cut into 13 cm x 13 cm pieces, which were superposed and heated at 2 kg / cm 2 and 50 ° C for 2 hours under pressure, then left to cool under pressure for 12 hours and taken out, and the test pieces adhered to each other. It was visually judged whether or not it was present.
【００３７】○ ： 試験片の付着あり × ： 試験片の付着なし ガラス転移点 動的粘弾性測定装置を使用してガラス転移温度Ｔｇ
（℃）を測定し、測定値で示した。これは樹脂膜の硬軟
を示す。◯: Adhesion of test piece ×: No adhesion of test piece Glass transition point Glass transition temperature Tg using a dynamic viscoelasticity measuring device
(° C.) was measured and indicated by the measured value. This indicates the hardness of the resin film.
【００３８】耐衝撃性 デュポン衝撃試験機にて室温下、１ｋｇ加重を高さ５０
ｃｍから落として衝撃を加え、塗膜の損傷の程度を目視
判定した。Impact resistance A room temperature of 1 kg is applied to a height of 50 with a DuPont impact tester at room temperature.
It was dropped from cm and an impact was applied, and the degree of damage of the coating film was visually judged.
【００３９】○ ： 塗膜切れなし × ： 塗膜切れあり 耐屈曲性 ４ｃｍ×５ｃｍの試験片を作成し、手で２つ折りにして
デュポン衝撃試験機特殊ハゼ折り型試験機にて室温下、
１ｋｇ加重を高さ５０ｃｍから落として折り曲げて、折
り曲げ部分の塗膜の亀裂の長さ及び亀裂の状態を目視判
定した。○: No coating film breakage ×: Coating film breakage Bending resistance A test piece of 4 cm × 5 cm was prepared and folded in two by hand at room temperature using a DuPont impact tester special goby folding type tester.
A load of 1 kg was dropped from a height of 50 cm and bending was performed, and the length of the crack and the state of the crack of the coating film at the bent portion were visually determined.
【００４０】○ ： 亀列０．３ｃｍ以下 × ： 亀列０．３ｃｍより大 耐レトルト性 試験片をレトルト釜に入れ、１３０℃、３０分間レトル
ト処理を施した後、塗膜の損傷程度を目視判定した。◯: 0.3 cm or less for turtle row ×: Greater than 0.3 cm for turtle row Retort resistance test pieces were put in a retort kettle and subjected to retort treatment at 130 ° C. for 30 minutes, and then the degree of damage to the coating film was visually observed. It was judged.
【００４１】Ａ ： 変化なし Ｂ ： 若干白化 Ｃ ： 白化 Ｄ ： 塗膜に損傷発生 保色性 試験片を１９０℃、１０分間追加加熱乾燥を行い、塗膜
の黄変度を目視判定した。A: No change B: Slight whitening C: Whitening D: Damage to coating film Color retention The test piece was additionally heated and dried at 190 ° C. for 10 minutes, and the degree of yellowing of the coating film was visually evaluated.
【００４２】○ ： 変化なし × ： 黄変 発煙性 １８０℃に加熱したホットプレート上に試験片を置き、
発煙の状況を目視観察した。○: No change ×: Yellowing Smoke emission The test piece was placed on a hot plate heated to 180 ° C.
The state of smoke generation was visually observed.
【００４３】○ ： 発煙なし × ： 激しく発煙○: No smoke generation ×: Vigorous smoke generation
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【発明の効果】本発明によれば、塗料として使用した場
合にブロッキングを起こす事がなく、また、有害物質の
残留を著しく低く押さえることによって、塗膜の耐溶剤
性や耐レトルト性の向上及び塗膜硬化時の有害物質の蒸
散防止を実現した酸変性エポキシ樹脂を提供できる。EFFECTS OF THE INVENTION According to the present invention, when used as a paint, blocking does not occur, and the residue of harmful substances is suppressed to a very low level to improve the solvent resistance and retort resistance of the coating film. It is possible to provide an acid-modified epoxy resin that prevents the evaporation of harmful substances when the coating film is cured.
Claims (6)
酸基を少なくとも２個含有するポリヒドロキシ化合物
（Ａ）の第２級水酸基とモノカルボン酸（Ｂ）とを反応
せしめて酸変性化合物を得る第１工程、次いでこれをエ
ポキシ化してエポキシ樹脂を得る第２工程、からなるこ
とを特徴とする酸変性エポキシ樹脂の製造方法。1. An acid-modified compound is obtained by reacting a secondary hydroxyl group of a polyhydroxy compound (A) having a secondary hydroxyl group and containing at least two phenolic hydroxyl groups with a monocarboxylic acid (B). A method for producing an acid-modified epoxy resin, comprising a first step and a second step of epoxidizing the epoxy resin to obtain an epoxy resin.
ェノール性水酸基を少なくとも２個含有するポリヒドロ
キシ化合物（Ａ）にモノカルボン酸（Ｂ）を反応させ、
第２級水酸基とモノカルボン酸が縮合した構造を有しか
つフェノール性水酸基を少なくとも２個含有する酸変性
化合物を得る工程であり、第２工程が、この酸変性化合
物にエポキシ基供給物質（Ｃ）を反応させて、第２級水
酸基とモノカルボン酸が縮合した構造を有しかつエポキ
シ基を少なくとも２個含有する酸変性エポキシ樹脂を得
る工程である請求項１記載の製造方法。2. The first step is to react a monocarboxylic acid (B) with a polyhydroxy compound (A) having a secondary hydroxyl group and containing at least two phenolic hydroxyl groups,
This is a step of obtaining an acid-modified compound having a structure in which a secondary hydroxyl group is condensed with a monocarboxylic acid and containing at least two phenolic hydroxyl groups, and the second step is to add an epoxy group-supplying substance (C 2. The method according to claim 1, which is a step of obtaining an acid-modified epoxy resin having a structure in which a secondary hydroxyl group and a monocarboxylic acid are condensed and containing at least two epoxy groups.
2ＣＨ（ＯＨ）ＣＨ2−結合または−ＣＨ2Ｃ（ＣＨ3）
（ＯＨ）ＣＨ2−結合とビスフェノール骨格の繰り返し
単位からなり、その末端がフェノール性水酸基であるポ
リヒドロキシ化合物で、エポキシ基供給物質（Ｃ）が、
ビスフェノールポリグリシジルエーテルである請求項２
記載の製造方法。3. The polyhydroxy compound (A) is --CH.
2 CH (OH) CH 2 - bond or -CH 2 C (CH 3)
A polyhydroxy compound having a (OH) CH 2 -bond and a repeating unit of a bisphenol skeleton, the terminal of which is a phenolic hydroxyl group, and the epoxy group supplying substance (C) is
A bisphenol polyglycidyl ether.
The manufacturing method described.
2ＣＨ（ＯＨ）ＣＨ2−結合または−ＣＨ2Ｃ（ＣＨ3）
（ＯＨ）ＣＨ2−結合とビスフェノール骨格の繰り返し
単位からなり、その末端がフェノール性水酸基であるポ
リヒドロキシ化合物で、エポキシ基供給物質（Ｃ）が、
ノボラック樹脂ポリグリシジルエーテルである請求項２
記載の製造方法。4. The polyhydroxy compound (A) is --CH.
2 CH (OH) CH 2 - bond or -CH 2 C (CH 3)
A polyhydroxy compound having a (OH) CH 2 -bond and a repeating unit of a bisphenol skeleton, the terminal of which is a phenolic hydroxyl group, and the epoxy group supplying substance (C) is
A novolac resin polyglycidyl ether.
The manufacturing method described.
である請求項１、２、３又は４記載の製造方法。5. The production method according to claim 1, wherein the monocarboxylic acid (B) is an unsaturated fatty acid.
以上の不飽和脂肪酸である請求項１、２、３又は４記載
の製造方法。6. The monocarboxylic acid (B) has an iodine value of 120.
The method according to claim 1, 2, 3, or 4, which is the above unsaturated fatty acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22075291A JPH0559148A (en) | 1991-08-31 | 1991-08-31 | Production of acid-modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22075291A JPH0559148A (en) | 1991-08-31 | 1991-08-31 | Production of acid-modified epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0559148A true JPH0559148A (en) | 1993-03-09 |
Family
ID=16755989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22075291A Pending JPH0559148A (en) | 1991-08-31 | 1991-08-31 | Production of acid-modified epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0559148A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257138A (en) * | 2005-03-15 | 2006-09-28 | Dainippon Ink & Chem Inc | Side-chain acryloyl group-containing epoxy resin and method for producing the same |
| WO2008035404A1 (en) * | 2006-09-20 | 2008-03-27 | Dic Corporation | Linear (meth)acryloyl-containing compound, star (meth)acryloyl-containing compound and process for producing them |
| JP2008069306A (en) * | 2006-09-15 | 2008-03-27 | Dainippon Ink & Chem Inc | Method for producing methacrylate-modified epoxy resin |
-
1991
- 1991-08-31 JP JP22075291A patent/JPH0559148A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257138A (en) * | 2005-03-15 | 2006-09-28 | Dainippon Ink & Chem Inc | Side-chain acryloyl group-containing epoxy resin and method for producing the same |
| JP2008069306A (en) * | 2006-09-15 | 2008-03-27 | Dainippon Ink & Chem Inc | Method for producing methacrylate-modified epoxy resin |
| WO2008035404A1 (en) * | 2006-09-20 | 2008-03-27 | Dic Corporation | Linear (meth)acryloyl-containing compound, star (meth)acryloyl-containing compound and process for producing them |
| KR101066132B1 (en) * | 2006-09-20 | 2011-09-20 | 디아이씨 가부시끼가이샤 | Linear methacryloyl-containing compound, star methacryloyl-containing compound and process for producing them |
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