JPH08176476A - Curing resin composition for cathodic electrodeposition coating - Google Patents
Curing resin composition for cathodic electrodeposition coatingInfo
- Publication number
- JPH08176476A JPH08176476A JP6336130A JP33613094A JPH08176476A JP H08176476 A JPH08176476 A JP H08176476A JP 6336130 A JP6336130 A JP 6336130A JP 33613094 A JP33613094 A JP 33613094A JP H08176476 A JPH08176476 A JP H08176476A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- parts
- acid
- curing agent
- electrodeposition coating
- 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
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- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明の硬化剤樹脂組成物は陰極
析出型電着塗料の硬化剤として用いられ、塗膜の物理性
能及び防錆性能を向上させることが出来る。BACKGROUND OF THE INVENTION The curing agent resin composition of the present invention is used as a curing agent for a cathodic deposition type electrodeposition coating composition and can improve the physical properties and rust preventive properties of a coating film.
【０００２】[0002]
【従来の技術】陰極析出型電着塗料は、自動車、電気器
具、農機具、鋼製家具、建築用資材等の金属製品の防
錆、耐食性を主な目的とした塗装に広く使用されてい
る。膜厚の均一性（特に袋状部分の内部にも十分塗装さ
れる）や、有機溶剤の含有量が少ないので、環境汚染が
少ない事や、自動で塗装が行える為、省人化が出来る等
の特徴を有している。2. Description of the Related Art Cathode deposition type electrodeposition coatings are widely used for coating mainly for rust prevention and corrosion resistance of metal products such as automobiles, electric appliances, agricultural machinery, steel furniture, and construction materials. Uniformity of the film thickness (especially well coated inside the bag-like part) and low content of organic solvent reduce environmental pollution, and automatic coating allows labor saving. It has the characteristics of
【０００３】[0003]
【発明が解決しようとする課題】近年、環境保全の必要
性が強まっている中、重金属や有機溶剤の含有量を減少
させて、より低公害化する事や、塗装膜厚を薄くして経
済性をより向上させることが要求されており、無公害型
の防錆剤の使用や有機溶剤に変わる可塑剤の使用の提案
や、従来より薄い膜厚で、十分な物理性能と防錆性能を
発揮するために塗料のバインダー部分を構成している基
剤樹脂組成物に、例えばキレート形成能を有し、金属と
の密着性を向上させる分子構造を導入する事や、同じく
硬化剤樹脂組成物に可撓性を付与するために、ポリアル
キレングリコールを始め柔軟な分子骨格を有するポリオ
ール変性のブロックイソシアネートを使用したりする提
案がなされている。しかし、一方で上記金属製品の性能
向上が進むにつれ、その耐久性、経済性等のレベルも高
くなってきており、電着塗膜も更に高度の防食性能や物
理性能が要求されている。これに対し、上記の硬化剤樹
脂組成物に可撓性ポリオール変性のブロックイソシアネ
ートを使用する場合には、可撓性を向上させるため、ポ
リオールの分子量を大きくしたり変性量を多くしたりす
る事が考えられるが、それによって物理性能は向上する
反面、防錆性能が低下するという欠点を有している。In recent years, with the increasing need for environmental protection, it is possible to reduce the content of heavy metals and organic solvents to further reduce pollution, and to reduce the coating film thickness to make it economical. There is a demand for further improvement in the properties, proposals for the use of pollution-free rust preventive agents and the use of plasticizers instead of organic solvents, and sufficient physical and rust preventive performance with thinner film thickness than before. The base resin composition that constitutes the binder portion of the coating material in order to exert the effect, for example, by introducing a molecular structure having a chelate-forming ability and improving adhesion with a metal, and also a curing agent resin composition In order to impart flexibility to the above, it has been proposed to use a polyol-modified blocked isocyanate having a flexible molecular skeleton such as polyalkylene glycol. However, on the other hand, as the performance of the above metal products has been improved, their durability, economical efficiency and the like have been increased, and the electrodeposition coating film is required to have higher anticorrosion performance and physical performance. On the other hand, in the case of using a flexible polyol-modified blocked isocyanate in the above-mentioned curing agent resin composition, in order to improve flexibility, increase the molecular weight of the polyol or increase the modification amount. Although this may improve the physical performance, it has a drawback that the anticorrosion performance is deteriorated.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、この問題
を解決し上記要求に応えるために、塗膜の物理性能及び
防食性能を同時に向上させる目的で、塗料のバインダー
成分を構成する硬化剤樹脂組成物の改良が必須で有ると
考え、鋭意検討した結果、本発明の硬化剤樹脂組成物の
発明に至った。In order to solve this problem and meet the above-mentioned requirements, the inventors of the present invention have set a curing agent that constitutes a binder component of a paint for the purpose of simultaneously improving the physical performance and anticorrosion performance of a coating film. Considering that improvement of the curing agent resin composition is essential, as a result of intensive studies, the invention of the curing agent resin composition of the present invention was achieved.
【０００５】即ち本発明は、脂肪酸とポリイソシアネー
トとの反応によるアマイド結合を分子内に有する陰極析
出型電着塗料用硬化剤樹脂組成物である。That is, the present invention is a curing agent resin composition for a cathodic deposition type electrodeposition coating composition having an amide bond in the molecule by the reaction of a fatty acid and a polyisocyanate.
【０００６】本発明の硬化剤樹脂組成物は脂肪族または
芳香脂肪族または芳香族のポリイソシアネート（ジイソ
シアネートを含む）のイソシアネート基の一部と脂肪酸
のカルボキシル基を反応させアマイド結合を形成させ、
残りのイソシアネート基をアルコール、アミン、アミ
ド、またはオキシム等通常の陰極析出型電着塗料用硬化
剤であるブロックイソシアネートに用いられる公知のブ
ロック剤と反応させて得る。The curing agent resin composition of the present invention reacts a part of the isocyanate group of an aliphatic or araliphatic or aromatic polyisocyanate (including diisocyanate) with a carboxyl group of a fatty acid to form an amide bond,
The remaining isocyanate group can be obtained by reacting with a known blocking agent used for a blocked isocyanate which is a usual curing agent for cathodic deposition type electrodeposition coating such as alcohol, amine, amide, or oxime.
【０００７】その硬化剤樹脂分子内に脂肪酸基とイソシ
アネート基の反応によるアマイド結合を含有させる事
で、脂肪酸による柔軟性や金属表面との良好な親和性と
アマイド結合による強靭性と金属への密着性を架橋塗膜
に付与する事が出来るので、塗膜の可撓性や耐衝撃性を
向上させる事が出来、さらに塗膜と金属との密着性も向
上させる事が出来る為、優れた物理性能や防錆性能を持
った陰極析出型電着塗膜を得る事が出来る。By including an amide bond by reaction of a fatty acid group and an isocyanate group in the curing agent resin molecule, flexibility by fatty acid, good affinity with metal surface, toughness by amide bond and adhesion to metal Properties can be imparted to the crosslinked coating film, the flexibility and impact resistance of the coating film can be improved, and the adhesion between the coating film and the metal can also be improved. It is possible to obtain a cathodic deposition type electrodeposition coating film having high performance and rust prevention performance.
【０００８】本発明では、かかるアマイド結合を形成す
る為の脂肪酸量を固形分換算で、硬化剤樹脂組成物中５
〜７０重量％含有するのが好ましい。５重量％未満では
十分な可撓性と防錆性能が得られず、７０重量％を超え
ると、本発明の硬化剤樹脂と組み合わせて陰極析出型電
着塗料のバインダー成分を構成するアミン変性の基剤樹
脂や、有機溶剤との相溶性が劣り、塗料の安定性が低下
するので好ましくない。In the present invention, the amount of fatty acid for forming such an amide bond is calculated in terms of solid content to be 5 in the curing agent resin composition.
It is preferably contained in an amount of up to 70% by weight. If it is less than 5% by weight, sufficient flexibility and rust preventive performance cannot be obtained, and if it exceeds 70% by weight, the amine-modified amine compound which constitutes the binder component of the cathodic deposition type electrodeposition coating composition in combination with the curing agent resin of the present invention is used. It is not preferable because the compatibility with the base resin and the organic solvent is poor and the stability of the coating composition is lowered.
【０００９】脂肪酸とポリイソシアネートとの反応は通
常１００〜１８０℃の温度で行うことが出来る。この時
必要に応じて、メチルエチルケトン、メチルイソブチル
ケトン、トルエン、キシレン、セロソルブアセテート等
イソシアネート基および脂肪酸に対して不活性な溶剤お
よび有機錫、アミン等の触媒を用いても良い。また窒素
ガス気流中で行うのが好ましい。また、アルコール、ア
ミン、アミド、またはオキシム等のブロック剤とポリイ
ソシアネートとの反応は通常３０〜１８０℃の温度で行
うことが出来る。この時も必要に応じて、上記の有機溶
剤及び触媒を用いても良い。またこれらの反応は、段階
的に行っても良いし、同時に行っても良い。The reaction between the fatty acid and the polyisocyanate can usually be carried out at a temperature of 100 to 180 ° C. At this time, if necessary, a solvent inert to isocyanate groups such as methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and cellosolve acetate and a fatty acid, and a catalyst such as organic tin and amine may be used. It is also preferable to carry out in a nitrogen gas stream. The reaction between a blocking agent such as alcohol, amine, amide, or oxime and polyisocyanate can be usually carried out at a temperature of 30 to 180 ° C. At this time also, if necessary, the above-mentioned organic solvent and catalyst may be used. Further, these reactions may be carried out stepwise or simultaneously.
【００１０】本発明において用いられる脂肪酸は一般に
ＣｎＨｍＣＯＯＨ（ｎ＝７〜１７、ｍ＝１５〜３５）で
表される飽和または不飽和の脂肪酸、及びこれらの２〜
４分子を熱重合させて得られるダイマー酸、トリマー酸
またはテトラマー酸である。飽和または不飽和の脂肪酸
としては、例えば大豆油脂肪酸、椰子油脂肪酸、ひまし
油脂肪酸、脱水ひまし油脂肪酸、あまに油脂肪酸、桐油
脂肪酸、ステアリン酸、オレイン酸、リシノール酸、リ
ノール酸、リノレイン酸、エレオステアリン酸、アビエ
チン酸等が挙げられる。またダイマー酸、トリマー酸及
びテトラマー酸は、上記の脂肪酸の熱重合で得られる
が、本発明では特に、これらの内Ｃ18の不飽和脂肪酸
（例えばリノール酸、脱水ひまし油脂肪酸等）の熱重合
で得られる２塩基酸、３塩基酸及び４塩基酸が好まし
い。The fatty acid used in the present invention is generally a saturated or unsaturated fatty acid represented by CnHmCOOH (n = 7 to 17, m = 15 to 35), and 2 to 5 of these fatty acids.
It is a dimer acid, trimer acid or tetramer acid obtained by thermally polymerizing 4 molecules. Examples of the saturated or unsaturated fatty acids include soybean oil fatty acid, coconut oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, linseed oil fatty acid, tung oil fatty acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, eleoleic acid. Examples include stearic acid and abietic acid. Further, dimer acid, trimer acid and tetramer acid can be obtained by thermal polymerization of the above-mentioned fatty acids, and in the present invention, in particular, they are obtained by thermal polymerization of C18 unsaturated fatty acids (eg linoleic acid, dehydrated castor oil fatty acid etc.). The dibasic acids, tribasic acids and tetrabasic acids mentioned are preferred.
【００１１】本発明に於いて用いられるポリイソシアネ
ートはトルイレンジイソシアネート、４、４´−ジフェ
ニルメタンジイソシアネート、キシリレンジイソシアネ
ート、テトラメチルキシリレンジイソシアネート、ヘキ
サメチレンジイソシアネート、イソホロンジイソシアネ
ート、１、３−もしくは１、４−シクロヘキサン−ジイ
ソシアネート等芳香族、芳香脂肪族、脂肪族、脂環族の
ジイソシアネートおよび／または、これらジイソシアネ
ートの２量体、３量体、ポリ（ジフェニルメタンジイソ
シアネート）および／または、これらジイソシアネート
とポリオールとのウレタン化反応生成物等が挙げられ
る。ここで言うポリオールとはエチレングリコール、ジ
エチレングリコール、ポリエチレングリコール、プロピ
レングリコール、ポリプロピレングリコール、トリメチ
ロールプロパン、グリセリン、ペンタエリスリトール等
が好ましい。The polyisocyanates used in the present invention are toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4. An aromatic, araliphatic, aliphatic or alicyclic diisocyanate such as cyclohexane-diisocyanate and / or a dimer or trimer of these diisocyanates, poly (diphenylmethane diisocyanate) and / or a diisocyanate and a polyol Examples thereof include urethanization reaction products. The polyol referred to herein is preferably ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, or the like.
【００１２】本発明の硬化剤樹脂組成物は、通常の電着
塗料の構成成分であるアミン変性エポキシ樹脂（特開昭
５４−４９７８号公報、特開昭５４−９３０２４号、特
開昭５３−４７１４３号公報、特開昭５３−８６７３号
公報、、特開昭５５−８０４３６号公報、特開昭５９−
２０６４４２号公報等参照）と混合して用いる。混合比
率は固形分換算で本発明の硬化剤樹脂組成物５〜５０重
量％、アミン変性エポキシ樹脂９５〜５０重量％が好ま
しい。上記樹脂混合物は通常、酸で中和して水分散型ま
たは水可溶性にして使用される。使用し得る酸は無機酸
または有機酸のいずれであってもよいが、有機酸が好ま
しい。例えば蟻酸、酢酸、プロピオン酸、乳酸、酪酸等
があげられる。The hardener resin composition of the present invention comprises an amine-modified epoxy resin (Japanese Unexamined Patent Publication No. 54-4978, Japanese Unexamined Patent Publication No. 54-93024, and Japanese Unexamined Patent Publication No. 53- 47143, JP-A-53-8673, JP-A-55-80436, and JP-A-59-
No. 206442). The mixing ratio is preferably 5 to 50% by weight of the curing agent resin composition of the present invention and 95 to 50% by weight of amine-modified epoxy resin in terms of solid content. The above resin mixture is usually neutralized with an acid to be used as a water dispersion type or water soluble type. The acid that can be used may be either an inorganic acid or an organic acid, but an organic acid is preferred. Examples thereof include formic acid, acetic acid, propionic acid, lactic acid, butyric acid and the like.
【００１３】本発明の硬化剤樹脂組成物を用いた陰極析
出型電着塗料組成物は硬化触媒として、有機錫化合物を
添加してもよく、その場合の含有量は金属に換算して樹
脂固形分に対し０．１〜５重量％、好ましくは０．１〜
１．０重量％である。本発明の樹脂組成物を用いた陰極
析出型電着塗料組成物はさらに必要に応じて顔料を配合
しても良い。例えば、酸化チタン、カーボンブラック、
亜鉛華、ベンガラ等の無機着色顔料や各種有機着色顔
料、珪酸アルミニウム、珪酸マグネシウム、硫酸バリウ
ム、炭酸カルシウム等の体質顔料、塩基性珪酸鉛、リン
モリブデン酸アルミニウム、燐酸亜鉛、トリポリ燐酸２
水素アルミニウム、モリブデン酸アルミニウム、モリブ
デン酸亜鉛等の防錆顔料が挙げられる。これらの顔料は
限定されない。本発明の硬化剤樹脂組成物を用いた陰極
析出型電着塗料組成物は、さらに必要に応じて通常電着
塗料に用いられる有機溶剤や添加剤（顔料分散剤、レオ
ロジー調整剤、紫外線吸収剤、消泡剤、ハジキ防止剤、
界面活性剤等）を添加してもよい。The cathodic deposition type electrodeposition coating composition using the curing agent resin composition of the present invention may contain an organic tin compound as a curing catalyst. 0.1 to 5% by weight, preferably 0.1 to 5%
It is 1.0% by weight. The cathode deposition type electrodeposition coating composition using the resin composition of the present invention may further contain a pigment, if necessary. For example, titanium oxide, carbon black,
Inorganic coloring pigments such as zinc white and red iron oxide, various organic coloring pigments, extender pigments such as aluminum silicate, magnesium silicate, barium sulfate and calcium carbonate, basic lead silicate, aluminum phosphomolybdate, zinc phosphate, tripolyphosphate 2
Examples include rust preventive pigments such as aluminum hydrogen, aluminum molybdate, and zinc molybdate. These pigments are not limited. Cathode deposition type electrodeposition coating composition using the curing agent resin composition of the present invention, further organic solvent and additives (pigment dispersant, rheology adjuster, ultraviolet absorber) usually used in electrodeposition coating as needed. , Antifoaming agent, anti-repellent agent,
A surfactant or the like) may be added.
【００１４】以下、実施例により本発明を具体的に説明
する。部及び％は、それぞれ重量部及び重量％を示す。The present invention will be specifically described below with reference to examples. Parts and% indicate parts by weight and% by weight, respectively.
【００１５】[0015]
〔実施例１〕（本発明の硬化剤樹脂組成物の製造） 攪拌装置、温度計、コンデンサーを備えた１リットル４
つ口フラスコにトリメチロールプロパン１モルとジフェ
ニルメタン−４、４’−ジイソシアネート３モルとから
合成される１分子中に３個のイソシアネート基を有する
ポリイソシアネート（分子量８８４）１７７部とメチル
イソブチルケトン１３８部を仕込み、撹拌化に大豆油脂
肪酸（酸価２００ｍｇＫＯＨ／ｇ）４４．５部とε−カ
プロラクタム４６．５部を投入する。窒素ガスをフラス
コ内に流しながら加熱し、１１０〜１３０℃で遊離のイ
ソシアネート基が０．１１ｍｅｑ／ｇ固形分になるまで
反応させた後、フェノキシプロパノール６部を加え、さ
らに反応を続け遊離のＮＣＯ基を消失させて固形６５％
の硬化剤樹脂組成物Ａを得た。このものの酸価を測定し
たところ０であった。[Example 1] (Production of curing agent resin composition of the present invention) 1 liter 4 equipped with a stirrer, thermometer, condenser
173 parts of polyisocyanate (molecular weight 884) having 3 isocyanate groups in one molecule synthesized from 1 mol of trimethylolpropane and 3 mol of diphenylmethane-4,4'-diisocyanate in a one-necked flask and 138 parts of methyl isobutyl ketone Then, 44.5 parts of soybean oil fatty acid (acid value 200 mg KOH / g) and 46.5 parts of ε-caprolactam are added for stirring. After heating while flowing nitrogen gas into the flask and reacting at 110 to 130 ° C. until the free isocyanate group became 0.11 meq / g solid content, 6 parts of phenoxypropanol was added and the reaction was further continued to give free NCO. 65% solid by eliminating groups
The curing agent resin composition A of was obtained. The acid value of this product was measured and found to be 0.
【００１６】〔実施例２〕（本発明の硬化剤樹脂組成物
の製造） 攪拌装置、温度計、コンデンサーを備えた１リットル４
つ口フラスコにポリＭＤＩ（１分子中の平均ＮＣＯ基数
２．８）１４０部とメチルイソブチルケトン１９２部、
ポリプロピレングリコール（平均分子量１０００）６１
部、大豆油脂肪酸（酸価２００ｍｇＫＯＨ／ｇ）６１部
を仕込み、窒素ガスをフラスコ内に流しながら加熱し、
１１０〜１３０℃で遊離のイソシアネート基が２．５ｍ
ｅｑ／ｇ固形分になるまで反応させた後、ε−カプロラ
クタム６３．５部、フェノキシプロパノール３０．５部
を加え、９０〜１１０℃で遊離のＮＣＯ基が消失するま
で反応をつづける。かかる方法で固形分６５％の硬化剤
樹脂組成物Ｂを得た。またこの物の酸価を測定したとこ
ろ０であった。[Example 2] (Production of curing agent resin composition of the present invention) 1 liter 4 equipped with a stirrer, thermometer, condenser
In a one-necked flask, 140 parts of poly MDI (average number of NCO groups in one molecule 2.8) and 192 parts of methyl isobutyl ketone,
Polypropylene glycol (average molecular weight 1000) 61
And 61 parts of soybean oil fatty acid (acid value 200 mgKOH / g) were charged and heated while flowing nitrogen gas into the flask,
Free isocyanate group 2.5m at 110-130 ℃
After reacting until eq / g solid content, 63.5 parts of ε-caprolactam and 30.5 parts of phenoxypropanol are added, and the reaction is continued at 90 to 110 ° C until the free NCO group disappears. By this method, a curing agent resin composition B having a solid content of 65% was obtained. The acid value of this product was measured and found to be 0.
【００１７】〔実施例３〕（本発明の硬化剤樹脂組成物
の製造） 攪拌装置、温度計、コンデンサーを備えた１リットル４
つ口フラスコにヘキサメチレンジイソシアネートの３量
体（イソシアヌレート体）１９７部、メチルイソブチル
ケトン部、ジブチル錫ラウレート部、アビエチン酸５７
部を仕込み、１１０〜１３０℃で遊離のイソシアネート
基が３．３ｍｅｑ／ｇ固形分になるまで反応させた後、
７０℃まで冷却し、この温度を保ちながらメチルエチル
ケトオキシム７２部を３０分間にわたり等速滴下し、更
に遊離のＮＣＯ基が消失するまで保温を続けた。かかる
方法にて固形分６５％の硬化剤樹脂組成物Ｃを得た。ま
たこの物の酸価を測定したところ０であった。[Example 3] (Production of curing agent resin composition of the present invention) 1 liter 4 equipped with a stirrer, thermometer, condenser
Hexamethylene diisocyanate trimer (isocyanurate) 197 parts, methyl isobutyl ketone part, dibutyl tin laurate part, abietic acid 57
And charged at 110 to 130 ° C. until free isocyanate groups reached 3.3 meq / g solid content,
After cooling to 70 ° C., 72 parts of methylethylketoxime was added dropwise at a constant rate over 30 minutes while maintaining this temperature, and the temperature was kept until the free NCO group disappeared. By this method, a curing agent resin composition C having a solid content of 65% was obtained. The acid value of this product was measured and found to be 0.
【００１８】〔比較例１〕（従来の硬化剤樹脂組成物の
製造） 攪拌装置、温度計、コンデンサーを備えた１リットル４
つ口フラスコにトリメチロールプロパン１モルとジフェ
ニルメタンー４、４’ージイソシアネート３モルとから
合成される１分子中に３個のイソシアネート基を有する
ポリイソシアネート（分子量８８４）１７７部とメチル
イソブチルケトン１２８部を仕込み、撹拌化にε−カプ
ロラクタム４７部を投入する。その後加熱し、１１０〜
１３０℃で遊離のイソシアネート基が０．８ｍｅｑ／ｇ
固形分になるまで反応させた後、メトキシプロパノール
１４部を３０分に渡り等速滴下し、更に遊離のＮＣＯ基
が消失するまで保温を続けた。かかる方法で固形６５％
の硬化剤樹脂組成物Ｄを得た。Comparative Example 1 (Production of Conventional Hardener Resin Composition) 1 liter 4 equipped with a stirrer, thermometer, condenser
173 parts of polyisocyanate (molecular weight 884) having 3 isocyanate groups in one molecule synthesized from 1 mol of trimethylolpropane and 3 mol of diphenylmethane-4,4'-diisocyanate in a two-necked flask and 128 parts of methyl isobutyl ketone Is charged, and 47 parts of ε-caprolactam is added for stirring. Then heat, 110-
0.8 meq / g of free isocyanate groups at 130 ° C
After reacting until a solid content was reached, 14 parts of methoxypropanol was added dropwise at a constant rate over 30 minutes, and the temperature was kept until the free NCO group disappeared. 65% solids in this way
To obtain a curing agent resin composition D.
【００１９】〔比較例２〕（従来の硬化剤樹脂組成物の
製造） 攪拌装置、温度計、コンデンサーを備えた１リットル４
つ口フラスコにポリＭＤＩ（１分子中の平均ＮＣＯ基数
２．８）１４０部とメチルイソブチルケトン１５２部、
ポリプロピレングリコール（平均分子量１０００）６１
部を仕込み、窒素ガスをフラスコ内に流しながら加熱
し、１１０〜１３０℃で遊離のイソシアネート基が２．
３ｍｅｑ／ｇ固形分になるまで反応させた後、ε−カプ
ロラクタム６３．５部、ブチルセロソルブ１８部を加
え、８０〜９０℃で遊離のＮＣＯ基が消失するまで反応
をつづける。かかる方法で固形分６５％の硬化剤樹脂組
成物Ｅを得た。Comparative Example 2 (Production of Conventional Curing Agent Resin Composition) 1 liter 4 equipped with a stirrer, thermometer, condenser
In a one-necked flask, 140 parts of poly MDI (average number of NCO groups in one molecule is 2.8) and 152 parts of methyl isobutyl ketone,
Polypropylene glycol (average molecular weight 1000) 61
Was charged and heated while flowing nitrogen gas into the flask, and at 110 to 130 ° C., free isocyanate groups were 2.
After reacting until the solid content becomes 3 meq / g, 63.5 parts of ε-caprolactam and 18 parts of butyl cellosolve are added, and the reaction is continued at 80 to 90 ° C until the free NCO group disappears. By this method, a curing agent resin composition E having a solid content of 65% was obtained.
【００２０】〔比較例３〕（従来の硬化剤樹脂組成物の
製造） 攪拌装置、温度計、コンデンサーを備えた１リットル４
つ口フラスコにヘキサメチレンジイソシアネートの３量
体（イソシアヌレート体）１９７部、メチルイソブチル
ケトン１５３部、ジブチル錫ラウレート０．２部を仕込
み、７０℃を保ちながらメチルエチルケトオキシム８７
部を６０分間にわたり等速滴下した後、遊離のＮＣＯ基
が消失するまで保温を続けて固形分６５％の硬化剤樹脂
組成物Ｆを得た。Comparative Example 3 (Production of Conventional Hardener Resin Composition) 1 liter 4 equipped with a stirrer, thermometer, condenser
A three-necked flask was charged with 197 parts of hexamethylene diisocyanate trimer (isocyanurate), 153 parts of methyl isobutyl ketone, and 0.2 parts of dibutyl tin laurate, and methyl ethyl ketoxime 87 was maintained at 70 ° C.
After 60 parts of the solution was added dropwise at a constant rate, the temperature was kept until the free NCO group disappeared to obtain a curing agent resin composition F having a solid content of 65%.
【００２１】（アミン変性エポキシ樹脂の製造）攪拌装
置、温度計、コンデンサーを備えた１リットル４つ口フ
ラスコにポリプロピレングリコールジグリシジルエーテ
ル（エポキシ当量３００）９１部とビスフェノールＡの
ジグリシジルエーテル２５３部とビスフェノールＡ１３
２部とトリブチルアミン０．２部を仕込み１５０℃でエ
ポキシ当量９５０まで反応させた後、１１０℃に冷却し
てメトキシプロパノール２２３部を加える。その後ジエ
タノールアミン４５部を加え、８０℃で２時間保温し、
固形分７０％のアミン変性エポキシ樹脂溶液を得た。(Production of amine-modified epoxy resin) 91 parts of polypropylene glycol diglycidyl ether (epoxy equivalent 300) and 253 parts of bisphenol A diglycidyl ether were placed in a 1 liter four-necked flask equipped with a stirrer, a thermometer and a condenser. Bisphenol A13
After charging 2 parts and 0.2 part of tributylamine and reacting at 150 ° C. to an epoxy equivalent of 950, the mixture was cooled to 110 ° C. and 223 parts of methoxypropanol was added. After that, 45 parts of diethanolamine was added, and the mixture was kept warm at 80 ° C for 2 hours.
An amine-modified epoxy resin solution having a solid content of 70% was obtained.
【００２２】試験例１〜３、比較試験例１〜３ 実施例１〜３、比較例１〜３で製造した硬化剤樹脂組成
物を用い、下記の配合で作成した電着塗料で鉄板を塗装
し各種テストを実施した。その結果表１の様に本発明の
硬化剤樹脂組成物を用いた試験例１〜３は、従来の硬化
剤樹脂組成物を用いた比較試験例１〜３に比べ、衝撃、
エリクセン、グラベロチッピング等の物性試験及びソル
トスプレー試験による防錆性で優秀な結果を示した。 アミン変性エポキシ樹脂 １００．０部 硬化剤樹脂組成物（Ａ〜Ｆ） ４６．０部 蟻酸 １．３部 ブチルカルビトール １３．０部 カーボンブラック ０．２部 酸化チタン １５．０部 カオリン １５．０部 塩基性珪酸鉛 ２．０部 ジブチル錫オキサイド ０．５部 脱イオン水 １４２２．０部 合計 １６１５．０部Test Examples 1 to 3, Comparative Test Examples 1 to 3 Using the hardener resin compositions produced in Examples 1 to 3 and Comparative Examples 1 to 3, iron plates were coated with an electrodeposition paint prepared by the following composition. Then various tests were conducted. As a result, as shown in Table 1, Test Examples 1 to 3 using the curing agent resin composition of the present invention are more impacted than Comparative Test Examples 1 to 3 using the conventional curing agent resin composition.
It showed excellent results in rust prevention by physical property tests such as Erichsen and gravero chipping and salt spray tests. Amine-modified epoxy resin 100.0 parts Curing agent resin composition (A to F) 46.0 parts Formic acid 1.3 parts Butyl carbitol 13.0 parts Carbon black 0.2 parts Titanium oxide 15.0 parts Kaolin 15.0 Parts Basic lead silicate 2.0 parts Dibutyltin oxide 0.5 parts Deionized water 1422.0 parts Total 1615.0 parts
【００２３】[0023]
【表１】 [Table 1]
【００２４】被塗物：燐酸亜鉛処理冷延鋼板（日本テス
トパネル社製 横７０ｍｍ、縦１５０ｍｍ、厚さ０．８
ｍｍ） 焼付け条件：１７０℃２０分 膜厚：２０μｍ 試験条件 ゲル分率：４０℃のメタノール／アセトン＝１／１（ｖ
ｏｌ）に試験板を２４時間浸漬した後の塗膜重量残存率 耐衝撃性：ＤｕＰｏｎｔ式、１／２”、１．５ｋｇ グラベロチップ：御影６号砕石、５００ｇ、４ｋｇ／ｃ
ｍ2 ＳＳＴ：ＪＩＳ Ｚ２３７１ 燐酸亜鉛処理冷延鋼板
１０００時間 クロスカットよりの錆幅（片幅）を表記Object to be coated: Zinc phosphate treated cold-rolled steel sheet (manufactured by Nippon Test Panel Co., Ltd., 70 mm wide, 150 mm long, 0.8 thick)
mm) Baking conditions: 170 ° C. for 20 minutes Film thickness: 20 μm Test conditions Gel fraction: 40 ° C. methanol / acetone = 1/1 (v
ol) the coating film weight residual rate after dipping the test plate for 24 hours Impact resistance: DuPont type, 1/2 ", 1.5 kg Gravelo chip: Mikage No. 6 crushed stone, 500 g, 4 kg / c
m 2 SST: JIS Z2371 zinc phosphate treated cold rolled steel sheet
1000 hours Indicate the rust width (single width) from the cross cut
【００２５】[0025]
【発明の効果】本発明の硬化剤樹脂組成物を用いること
により、陰極析出型電着塗膜の耐衝撃性、エリクセン、
耐チッピング性等の物理的性能及び防錆性能を著しく向
上させることが出来る。By using the curing agent resin composition of the present invention, the impact resistance of the cathodic deposition type electrodeposition coating film, Erichsen,
Physical performance such as chipping resistance and rust prevention performance can be significantly improved.
Claims (1)
よるアマイド結合を分子内に有する陰極析出型電着塗料
用硬化剤樹脂組成物。1. A curing agent resin composition for a cathodic deposition type electrodeposition coating, which has an amide bond in the molecule by the reaction of a fatty acid and a polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6336130A JPH08176476A (en) | 1994-12-22 | 1994-12-22 | Curing resin composition for cathodic electrodeposition coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6336130A JPH08176476A (en) | 1994-12-22 | 1994-12-22 | Curing resin composition for cathodic electrodeposition coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08176476A true JPH08176476A (en) | 1996-07-09 |
Family
ID=18296013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6336130A Pending JPH08176476A (en) | 1994-12-22 | 1994-12-22 | Curing resin composition for cathodic electrodeposition coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08176476A (en) |
-
1994
- 1994-12-22 JP JP6336130A patent/JPH08176476A/en active Pending
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