JPH01301768A - Low-temperature curing type electrodeposition coating resin composition - Google Patents

Low-temperature curing type electrodeposition coating resin composition

Info

Publication number
JPH01301768A
JPH01301768A JP13158488A JP13158488A JPH01301768A JP H01301768 A JPH01301768 A JP H01301768A JP 13158488 A JP13158488 A JP 13158488A JP 13158488 A JP13158488 A JP 13158488A JP H01301768 A JPH01301768 A JP H01301768A
Authority
JP
Japan
Prior art keywords
resin
mixed alkyl
alkyl etherified
groups
polycarboxylic 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.)
Granted
Application number
JP13158488A
Other languages
Japanese (ja)
Other versions
JP2543746B2 (en
Inventor
Tsutomu Nishimura
勉 西村
Yasuo Saito
斉藤 安雄
Yoshitaka Mizushima
水嶋 佳孝
Yoichi Fujiwara
陽一 藤原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Cyanamid Ltd
Honny Chemicals Co Ltd
Original Assignee
Mitsui Cyanamid Ltd
Honny Chemicals Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsui Cyanamid Ltd, Honny Chemicals Co Ltd filed Critical Mitsui Cyanamid Ltd
Priority to JP63131584A priority Critical patent/JP2543746B2/en
Publication of JPH01301768A publication Critical patent/JPH01301768A/en
Application granted granted Critical
Publication of JP2543746B2 publication Critical patent/JP2543746B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Paints Or Removers (AREA)

Abstract

PURPOSE:To obtain the subject composition, consisting of a polycarboxylic acid resin and a specific mixed alkyl etherified methylolmelamine resin and capable of reducing baking temperature and suppressing emission of formalin. CONSTITUTION:The objective composition obtained by blending (A) 50-95pts.wt. polycarboxylic acid resin with (B) 50-5pts.wt. mixed alkyl etherified methylolmelamine resin respectively having average <5 combined formaldehyde content, 1.0-3.5 methyl ether groups, 0.5-3.0 butyl ether groups, 0.5-3.0 imino groups and <0.5 methyol group per melamine nucleus and 1.5-3.5 average polymerization degree of the melamine nucleus with methanol, ethanol, etc., as an organic solvent, stirring and mixing the resultant blend. Furthermore, when the obtained composition is used as an electrodeposition coating, an organic amine and ammonia are added to make the polycarboxylic acid resin dispersible in water and the resultant resin is diluted with water for use.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は低温硬化型′電層塗料づ幻脂組ノ或物に関し、
更に―・シ<は、混合アルキルエーテル化メチロールメ
ラミン側111全架倫炸」とする低温硬化型屯漕塗料但
1崩組J戎物に関する。
[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a low-temperature curing type electrical layer coating and a resin composition.
Furthermore, the present invention relates to a low-temperature curing type paint with a mixed alkyl etherified methylol melamine side (111), which is a mixture of alkyl etherified methylol melamine.

〔従来の技術〕[Conventional technology]

電着塗装は、複雑な形状を廟する被塗物にも均一に墜装
ができ2又塗装効率に優れ美鹿な外観かえられる寺のオ
リ点があり、多くの産業分野で実施されている。セして
′電着塗装に使用される樹脂組成物としてポリカルボン
敵樹脂と架橋剤としてのメラミン樹脂との組成物が実用
きれ、メラミン核1個としてメチルエーテル化メチロー
ルメラミン樹脂又はブチルエーテル化メチロールメラミ
ン街脂が知られている。更に架橋剤の′亀看共進性の点
から混合アルキルエーテル化メチロールメンミノ樹脂を
使用することが提案されているか、塗膜の焼付けにより
高錨度盆必侠とする欠点がめり、これ全解決するために
低昌焼句は回部な水性塗料出聞脂組J必物の架橋剤とし
て、メラミン核1個当り平均50個以上の結合ホルムア
ルデヒド、XP−均0.2〜0゜8個の遊離メチロール
基金もち、メツノールとブタノールによって混合アルキ
ルエーテル化されたメチロールメラミン樹)猶を便用す
ることが従来されている(%開昭54−120641号
公報参照)。
Electrodeposition coating has the advantage of being able to uniformly coat objects with complex shapes, offering excellent bifurcated coating efficiency and giving a beautiful appearance, and is used in many industrial fields. . As a resin composition used for electrodeposition coating, a composition of polycarbonate resin and melamine resin as a crosslinking agent has been put into practical use, and one melamine nucleus is methyl etherified methylol melamine resin or butyl etherified methylol melamine resin. Street fat is known. Furthermore, it has been proposed to use a mixed alkyl etherified methylolmemino resin in view of the co-progressivity of the cross-linking agent, and the drawback that the baking of the coating film requires a high anchorage temperature has been realized, and this problem has been completely solved. In order to do this, low-shang pottery is used as a necessary cross-linking agent for water-based paints, with an average of more than 50 formaldehyde bonds per melamine nucleus, and an average of 0.2 to 0.8 formaldehyde bonds per melamine nucleus. It has been conventionally known to use a methylol melamine resin containing free methylol and mixed alkyl etherification with metsunol and butanol (see Japanese Patent Publication No. 120641/1982).

しかしながら、前記混合アルキルエーテル化メチロール
メラミン樹J猶會架橋剤として通常の上層塗装及び焼付
は条件で使用した場合、焼付温度が1501:未満では
得られる塗膜の硬度が未だ不光分であり、満足しうる耐
柴品性、耐溶剤性を有する塗膜が得られず、又結合ホル
ムアルデヒドが多いために、焼付時に発生するホルムア
ルデヒドが多く、著しく作業環境を損ねるという問題が
あった。
However, when the above-mentioned mixed alkyl etherified methylol melamine resin is used as a crosslinking agent under the conditions of normal upper layer coating and baking, the hardness of the resulting coating film is still unsatisfactory if the baking temperature is less than 1501: However, since a coating film with good chemical resistance and solvent resistance cannot be obtained, and since there is a large amount of bound formaldehyde, there is a problem that a large amount of formaldehyde is generated during baking, which significantly impairs the working environment.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

本発明の目的は、150℃未満の低温硬化が可能で、か
つ物理的性質が優れた電着塗膜を形成しつる電層塗料樹
脂組成物全提供することである。
An object of the present invention is to provide an electrical coating resin composition that can be cured at a low temperature of less than 150° C. and forms an electrodeposition coating film with excellent physical properties.

〔問題全解決するための手段〕[Means to solve all problems]

本発明について截置すると、本発明の低幌硬化型竜看塗
料慟脂組成物は(a)ポリカルボン眩樹脂50〜95亀
祉部、及び(b)メラミン核1個当り平均5個未満の結
合ホルムアルデヒド、10〜五5イ固のメチルエーテル
基、15〜3.041Jのッチルエーテル基、0.5〜
3.0個のイミノ基、15個未満のメチロール基’(r
 7pし、かつメラミン核の平均重合度が1.5〜3.
5である混合アルキルエーテル化メチロールメラミン腐
脂50〜5車量都よりなること金時徴とする。
To explain the present invention in detail, the low porosity hardening type lumber paint composition of the present invention has (a) a polycarbonate resin of 50 to 95 parts, and (b) an average of less than 5 melamine nuclei per one melamine nucleus. Bound formaldehyde, methyl ether group of 10-55 solids, methyl ether group of 15-3.041 J, 0.5-
3.0 imino groups, less than 15 methylol groups' (r
7p, and the average degree of polymerization of the melamine core is 1.5 to 3.
50 to 50% of mixed alkyl etherified methylolmelamine fat.

本発明者等の研死によると、′電層塗膜の級化に必要な
焼付温度は、架橋剤として使用するメラミン樹脂の構造
2特にメラミン核1個当りのイミノ基の個数に大きく影
響されるという知見を得た。本発明は、この知見に基づ
きなされたもので、次に示す符定のメラミン樹脂を架橋
剤として使用することにより低温硬化性に優れ、又塗膜
焼付時のホルマリンの発生が少なく、シかも塗膜物性の
優れた′亀N塗料@崩組成物全提供する目的を達成した
ものである。
According to research conducted by the present inventors, the baking temperature required for grading the electrolyte coating film is greatly influenced by the structure of the melamine resin used as a crosslinking agent, especially the number of imino groups per melamine nucleus. We obtained the knowledge that The present invention was made based on this knowledge, and by using the melamine resin shown below as a crosslinking agent, it has excellent low-temperature curing properties, generates less formalin when baking the paint film, and is easy to coat. This has achieved the objective of providing a ``Kame-N paint@degradable composition'' with excellent film properties.

本発明をよジ評細に直曲すると、(a)成分のポリカル
ボン酸1ηf)宿としては、通常、電着塗料用として1
史用される酸1曲15〜200のカルボキシル基に有す
るアクリル系樹脂、ポリエステル樹脂、アルキンド糸樹
jTh % 叡変注ポリブタ7エン系樹脂が挙げられる
A more detailed evaluation of the present invention reveals that (a) component polycarboxylic acid 1ηf) is usually used for electrodeposition paints as a 1ηf host.
Examples include acrylic resins, polyester resins, and polybutane-based resins having 15 to 200 carboxyl groups.

(切成分の混合アルキルエーテル化メチロールメラミン
樹脂は前占己した相定の構造因子により特徴づけられ、
符にメラミン核1個当り平均5個未満の結合ホルムアル
デヒド、  cL5〜3.0個のイミノ基及びメラミン
核の平均型8度15〜五5の相関関係により、随伴する
遊離ホルムアルデヒドの扉全低減し、低鴎硬化金可能に
する。
(The mixed alkyl etherified methylol melamine resin of the cutting component is characterized by a pre-occupied phase-determined structure factor,
Due to the average of less than 5 bound formaldehyde per melamine nucleus, cL5 ~ 3.0 imino groups and the average type 8 degree 15 ~ 55 correlation of the melamine nucleus, the accompanying free formaldehyde is completely reduced. , making low mold hardening possible.

又、メチルエーテル基は、メラミン核1個当り1.0〜
3.5個、好1しくは1.5〜5.0個、ブチルエーテ
ル基は05〜3.01固、好筐しくけ1.0〜2.0個
の範囲のものが適当である。
In addition, the number of methyl ether groups is 1.0 to 1 per melamine nucleus.
The number of butyl ether groups is preferably 0.5 to 3.01, preferably 1.0 to 2.0.

ブチルエーテル基がAD個より多くなると。When the number of butyl ether groups becomes more than AD.

メラミン樹脂の疎水・註が強くなり、ポリカルボンば樹
脂と分離するi川向が大となジ、電着浴の安定性に欠け
るために望1しくなく5一方05個未7^、更にはメチ
ルエーテル基単独になると、1杭着塗装の除に共進性が
悪くなり、亀肴浴甲に蓄積して浴組成のバランスがくす
れる結果をもたらし、又このようなメラミン粥;逍?用
いて′電着塗装した塗膜は焼付けに際し塗膜表面Vこ′
はしさ”ないしはクレータ−が発生するので@記割合の
範囲の混合アルキルエーテル化度が必須である。
The hydrophobicity of melamine resin becomes stronger, and the direction of separation from polycarbonate resin increases, which is undesirable due to the lack of stability of the electrodeposition bath, and furthermore, methyl When the ether group is used alone, the co-advance property becomes worse than that of the one-pile coating, and it accumulates in the bath shell, resulting in an imbalance in the bath composition. The coating film that was electrodeposited using this method has a surface V during baking.
Since rashes or craters occur, it is essential to have a degree of mixed alkyl etherification within the range shown in the figure below.

イミノ基はメラミン核1個当り0.5〜3.0個、好1
しくは0,5〜1.5 ([ilの範囲が適当であり、
焼付温度の低温化全可能にする。該イミノ基が115個
未満の場合には焼付温度の低温化が困難となり5一方3
個を超えると、塗膜の耐水性、耐敵性等の物理的性質が
低下するため好ましくない。メチロール基は、メラミン
核1個当り0.5個未満が適当である。メチロール基が
cL5個以上となると塗装時に発生するホルマリン蓋が
多く7iニジ作業環境上好葦しくない。
The number of imino groups is 0.5 to 3.0 per melamine nucleus, preferably 1
or 0.5 to 1.5 ([il range is appropriate,
Enables lower baking temperatures. If the number of imino groups is less than 115, it becomes difficult to lower the baking temperature.
If it exceeds 1,000,000, the physical properties such as water resistance and enemy resistance of the coating film will deteriorate, which is not preferable. The number of methylol groups is suitably less than 0.5 per melamine nucleus. When the number of methylol groups is 5 or more, a large amount of formalin is generated during coating, which is not favorable for the working environment of 7i Niji.

(1)) K分の混合アルキルエーテル化メチロールメ
ラミン樹脂としては、@1lii己のように1個のメラ
ミン核にメチルエーテル基、ブチルエーテル基、イミノ
基及びメチロール基をそれぞれの数値範囲で具備する樹
脂を生成する条件下で製造したいわゆる単一バッチの生
成樹脂の他に該混合アルキルエーテル化メチロールメラ
ミン’fil BWとメチルエーテル化メチロールメラ
ミン樹脂、ブチルエーテル化メチロールメラミン樹脂、
本発明で特定する範囲外の混合アルギルエーテル化メチ
ロールメラミン樹脂よりなる群から選ばれた少なくとも
1極との混合物であっても良く(ただし、混合物のメラ
ミン核11固当り半均の結合ホルムアルデヒド、メチル
エーテル基、ブチルエーテル基、イミノ基、メチロール
基の数及びメラミン核の平均電合度が本発明で待足する
範囲内であること金要する。)、又製造条件により単核
体と多核体の混合物であっても前記待ポする範囲内であ
れば使用できる。
(1)) As a mixed alkyl etherified methylol melamine resin with a K content, a resin having a methyl ether group, a butyl ether group, an imino group, and a methylol group in one melamine nucleus in the respective numerical ranges, such as @1lii. In addition to the so-called single-batch product resin produced under conditions producing the mixed alkyl etherified methylol melamine 'fil BW, methyl etherified methylol melamine resin, butyl etherified methylol melamine resin,
It may also be a mixture with at least one pole selected from the group consisting of mixed algyl etherified methylol melamine resins outside the range specified in the present invention (however, half the amount of bound formaldehyde, methyl The number of ether groups, butyl ether groups, imino groups, methylol groups and the average electrical degree of the melamine nucleus must be within the range required by the present invention.) Also, depending on the manufacturing conditions, a mixture of mononuclear and polynuclear Even if there is, it can be used as long as it is within the waiting range.

本発明における混合アルキルエーテル化メチロールメラ
ミン街脂は、概括的にはクリえは次のようにして製造さ
れる。
The mixed alkyl etherified methylolmelamine street fat in the present invention is generally produced as follows.

メラミンとホルムアルデヒドと全塩基性来件下で加熱し
、メチロールメラミン全合成する。
Methylolmelamine is synthesized by heating melamine and formaldehyde under a totally basic condition.

次いで、これにメタノール及びブタノール全力1」えて
赦性采件下で反応式せて人造する。
Next, methanol and butanol are added to this to create a reaction under controlled conditions.

別の方法として、該メチロールメラミンにメタノールの
みを加えて敵性条件下で反応させメチルエーテル化メチ
ロールメラミン樹脂とし、次に該メチルエーテル化メチ
ロールメラミン樹脂にブタノール全力え咳注条件下でエ
ーテル交換反応により製造する。
Another method is to add only methanol to the methylol melamine and react under hostile conditions to obtain a methyl etherified methylol melamine resin, and then to the methyl etherified methylol melamine resin by an ether exchange reaction under conditions of butanol. Manufacture.

本発明の電層塗料樹脂組成物は前記(a)成分と(1)
)成分と全塗膜形成成分とするものであり、両者の混合
割合は、(り成分50〜95M量部、好1しくは60〜
90重扉部に対しく1))成分5〜50重量部、好1し
くは10〜40重量部が適当である。
The electrolayer coating resin composition of the present invention comprises the above-mentioned component (a) and (1)
) component and the total coating film forming component, and the mixing ratio of both is 50 to 95 M parts, preferably 60 to 95 M parts of (component).
A suitable amount of component 1) is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 90-fold door part.

本発明の樹脂組成物は1例えば、かくはん機、温度計金
偏えた容器に、(a)ポリカルボン岐樹脂、(1)l混
合アルキルエーテル化メチロールメラミン樹脂及び有機
浴剤全入れた後、かくはん全行い十分に混合して調製す
る。
The resin composition of the present invention is prepared by putting (a) polycarbonate branched resin, (1) mixed alkyl etherified methylol melamine resin, and organic bath agent into a container equipped with a stirrer and a thermometer, and then stirring. Prepare by thoroughly mixing all steps.

有@浴剤としては、例えばメタノール5エタノール、n
−プロパノール、インクロビルアルコール、n−ブタノ
ール、インブタノールi 5ec−ブタノール、t−ブ
タノール、ペンタノール等のようなアルコール餉、メテ
ルセロンルブ、エテルセロンルブ、イングロビルセロン
ルブ、ブテルセロンルブ、、5eC−ブテルセロンルブ
寺のようなセロンルブ等全使用する。
Examples of bath additives include methanol, 5 ethanol, n
-Alcohols such as propanol, incrovir alcohol, n-butanol, imbutanol, 5ec-butanol, t-butanol, pentanol, etc., metelseron rub, etelseron rub, inglovir seron rub, buterseron rub, 5eC-buterseron rub, etc. I use all the seronlube etc.

本発明の樹脂組成vlを電層塗装用塗料とする場合、有
機アミン及び/又はアンモニアケ添加してポリカルボン
醒樹脂τ水分−敵可)]ヒとした俵、水を加えて適当な
樹脂向形分に希釈して使用する。この有機アミン及び/
又はアンモニアの添力[」は、ポリカルボ/叡と混合ア
ルキルエーテル化メチロールメラミン街脂と全混合する
前、混合と同時又は混合後に行うことができる。
When the resin composition Vl of the present invention is used as a coating material for electrolayer coating, an organic amine and/or ammonia solution is added to the polycarbonate resin τ (moisture-free)], and then the resin composition is prepared by adding water to a damp bale and adding water to the resin composition. Use by diluting to the desired amount. This organic amine and/or
Alternatively, the addition of ammonia can be carried out before, simultaneously with, or after the complete mixing of the polycarboxylic acid and the mixed alkyl etherified methylolmelamine street resin.

前6己ポリカルボン酸樹脂を水分散り龍とするために使
用するアンモニア又は有機アミンとしては、アンモニア
、モノメチルアミン、ジメチルアミン、トリメチルアミ
ン、モノエテルアはン、ジエチルアミン、トリエチルア
ミン、モノエタノールアミン、ジインプロピルアミン。
The ammonia or organic amine used to make the polycarboxylic acid resin water-dispersible includes ammonia, monomethylamine, dimethylamine, trimethylamine, monoetheramine, diethylamine, triethylamine, monoethanolamine, and diimpropylamine.

トリエタノールアミン、モノブチルアミン類、ジブチル
アミン類及びトリブチルアミンMWのようなアルキルア
ミン、モノエタノールアミン、ジェタノールアミン、ト
リエタノールアミン、モノインプロパツールアミン、ジ
イングロノくノールアミン、トリインクロバノールアミ
ン、ジメチルアミノエタノール及びジエチルアミノエタ
ノール等のようなアルカノールアミン、エチレンジアミ
ン、グロビレンジアミン、ジエチレントリアミン及びト
リエチレンテトラミン等のようなアルギレンボリアミン
、エチレンイミン及びグロビレンイミン等のようなアル
キレンイミン、ピペラジン、モルホリン、ピラジン及び
ピリジン等がある。
Alkylamines such as triethanolamine, monobutylamines, dibutylamines and tributylamine MW, monoethanolamine, jetanolamine, triethanolamine, monoimpropaturamine, diingronochunolamine, triinbanolamine, dimethyl Alkanolamines such as aminoethanol and diethylaminoethanol, alkyleneimines such as ethylenediamine, globylenediamine, diethylenetriamine and triethylenetetramine, alkyleneimines such as ethyleneimine and globyleneimine, piperazine, morpholine, pyrazine and pyridine. etc.

又、電着塗装用塗料調製時に、電層塗装に常用される着
色剤例えば涜色用染料、顔料、体買顔料、艷消剤、及び
硬化触媒、その他の添加剤例えば界面宿性剤、酸化防止
剤、紫外線吸収剤を配合してもよい。
In addition, when preparing paints for electrodeposition coating, colorants commonly used in electrocoating, such as staining dyes, pigments, body pigments, erasing agents, and curing catalysts, and other additives, such as interfacial holding agents, oxidizing agents, etc. An inhibitor and an ultraviolet absorber may be added.

前記の方法により調製した塗料浴中で、鉄、鋼、アルミ
ニウム及びこれらの表向に公知の化成処理を施したもの
、更にけ陽極ば化アルミニウム等の′電橋・性物品全′
屯看塗装すると1物品の形状、大ささにかかわらず均一
な奄堝−塗膜か得られる。
In the paint bath prepared by the above method, iron, steel, aluminum, those whose surfaces have been subjected to known chemical conversion treatments, and anodized aluminum, etc.
When the coating is applied, a uniform coating film can be obtained regardless of the shape and size of the article.

〔実施例〕〔Example〕

以下5本兄明金具体的に説明するため実施例を示す。な
お、実施例中の「都」及び「嘱」は、それぞれ重量部及
び重重%を示す。
Hereinafter, examples will be shown to specifically explain the five main brothers. In addition, "To" and "嘱" in Examples indicate parts by weight and weight %, respectively.

メラミン樹脂の製造例 製造剃1 温度計、攪拌機及び還流冷却器金偏えた1tの四つ目フ
ラスコにメラミン126 ? (1,0モル)及び80
%パラホルム168.75 F (4,5モル)及びメ
タノール520 ? (10,0モル)全入れ、20%
苛性ソーダ水fB7fでpH19,0〜9.5に調整し
た後、還流下で60分反応させた0及応終了俊内扇全3
0℃藍で冷却し、50%’IA 7926 mlを力■
え35℃で60分メチルエーテル化反比、全行った。反
応終了後20%苛性ソーダ水浴水浴液金工反応数のpH
をZ5〜105に脚歪し、次いで常圧接縮全行い、メタ
ノール全留去し、内幌が80℃に迷したら減圧下で跋縮
し、完全にメタノール全留去した。次に内温を60℃ま
で冷却した佼、メタノール320y(10,oモル)を
加え、35℃に保ち、50%憾酸26−を加え、60分
再びメチルエーテル化反応を行った後、20%苛性ソー
ダ水浴准全加え、反応液のpH全95〜1α5に調整し
、前述同様の常圧譲縮及び減圧譲縮全行いメタノールを
完全に糸外に留去した。
Production example of melamine resin Production shaver 1 Melamine 126 in a 1 ton four-eye flask with a thermometer, stirrer and reflux condenser. (1,0 mol) and 80
% paraform 168.75 F (4,5 mol) and methanol 520? (10,0 mol) all added, 20%
After adjusting the pH to 19.0 to 9.5 with caustic soda water fB7f, it was reacted for 60 minutes under reflux.
Cool at 0℃ and add 7926 ml of 50% IA.
The methyl etherification reaction was carried out at 35°C for 60 minutes. 20% caustic soda water bath after completion of reaction pH of liquid metalworking reaction number
was compressed to Z5 to 105, and then all methanol was distilled off under normal pressure. When the inner hood reached 80°C, it was compressed under reduced pressure to completely distill off all methanol. Next, the internal temperature was cooled to 60°C, 320y (10,0 mol) of methanol was added, kept at 35°C, 50% acetic acid was added, and the methyl etherification reaction was carried out again for 60 minutes. % caustic soda water bath, the pH of the reaction solution was adjusted to 95 to 1α5, and the same atmospheric pressure compression and vacuum compression as described above were carried out to completely distill methanol out of the thread.

次いで内扇を60℃丑で冷却した後ブタノ−#277.
5 S’ (3,75%#) f7+1工、 45℃に
保ちながら50%仇ば4.5dを加え、2時間エーテル
交換反応を行った。反応終了佐、20%苛性ンーダ水溶
故によりpH’i9.5〜1[15に調整し、中和塩が
析出し、プクノール臭がしなくなる葦で、減圧護ゐ全行
った佐内輻全80℃葦で冷却し、希釈用イングロバノー
ル90. Of(1,5モル)?加え、吸引f過により
中和塩を除去し、不揮発分795%の混合アルキルエー
テル化メチロールメラミン&J&(A−1)k得た。こ
の製品の分析結果全第1表に示す。
Then, after cooling the inner fan at 60°C, the butano #277.
5S'(3.75%#) f7+1 was added with 4.5d of 50% while maintaining the temperature at 45°C, and an ether exchange reaction was carried out for 2 hours. After the reaction was completed, the pH'i was adjusted to 9.5 to 1 [15] due to the 20% caustic powder dissolved in water, and the neutralized salt was precipitated and the Pukunor odor was removed. Cool with reeds and dilute with ingubanol 90. Of(1,5 mol)? In addition, the neutralized salt was removed by suction filtration to obtain a mixed alkyl etherified methylolmelamine &J&(A-1)k with a nonvolatile content of 795%. The complete analysis results of this product are shown in Table 1.

製造例2 製造例1で80%パラホルム1187.5r(5,0モ
ル)、及び希釈相インプロバノール全114f(1,9
モル)に替え、他は同様にして不揮発分8115%の混
合アルキルエーテル化メチロールメラミンat脂(A−
2)を得た。この製品の分析結果全第1表に示す。
Production Example 2 In Production Example 1, 80% paraform 1187.5r (5.0 mol) and diluted phase Improbanol total 114f (1.9
mol), and mixed alkyl etherified methylolmelamine at fat (A-
2) was obtained. The complete analysis results of this product are shown in Table 1.

比較製造例1 製造例1で80%パ2ホルムを5oor(s、。Comparative manufacturing example 1 In Production Example 1, 80% pa2form was added for 5 oor(s).

モル)及び希釈用イングロバノール(i790. Of
’(1,5モル)に替え、他は同様にして不う11発分
85.5%の混合アルキルエーテル化メチロールメラミ
ン樹脂(B−1)k得た。この製品の分析結果を第1表
に示す。
molar) and ingubanol for dilution (i790. Of
' (1.5 mol), but in the same manner as above, another 11 batches of mixed alkyl etherified methylol melamine resin (B-1) with a yield of 85.5% was obtained. The analysis results of this product are shown in Table 1.

実施汐01 かくはん磯、温度計を備えた3tフラスコ中に、市販の
アクリル糸ポリカルボン敵位11信浴液(神品名 コー
クンクスWE152  iし社製:駕脂固形分60軍量
楚、カルボキシル基中相隣9117都、混合アルキルエ
ーテル化メチロールメラミン樹脂(A−1−芸n)38
部全仕込牟、50℃で60分間かくはんを行い均一に混
合し電着塗料樹脂組成物全得た。ついで、脱イオン水8
45部を加えて樹脂固形分10重星予の′螺着塗料を調
製した。
In a 3t flask equipped with a stirrer and a thermometer, add a commercially available acrylic thread polycarbonate 11 salt bathing liquid (sacred product name Kokunkusu WE152, made by Ishisha: solid content of fat 60%, carboxyl group) Mixed alkyl etherified methylol melamine resin (A-1-Gei-n) 38
The entire mixture was mixed uniformly by stirring at 50° C. for 60 minutes to obtain a complete electrodeposition coating resin composition. Next, deionized water 8
45 parts were added to prepare a screw paint having a resin solid content of 10 double stars.

比較例1 実施例1の方法において、混合アルキルエーテル化メチ
ロールメラミン樹脂全比教製造し1j1で調製したB−
135都に変えた以外は、すべて回し方法全行い′東漸
塗料全調製した。
Comparative Example 1 In the method of Example 1, mixed alkyl etherified methylol melamine resin B-
Except for changing the color to 135, all the methods were followed and all preparations were made for Tozen paint.

実施力2 かくはん磯%温度計を設えた3tフラスコ中に、市販の
アクリル糸ポリカルボン敵側脂浴液(商品名  コータ
ソクスWE152  東し社製)85都、混合アルキル
エーテル化メチロールメラミン(A−1)28部、イン
プロビルアルコール20部を仕込み、30℃で10分間
かくはんを行い、ついで脱イオン7X40部をn1えて
更に10分間かくはんした。これに酸化チタン(商品名
 クイベークCR−90石原産業社製)27部とガラス
ビーズ200部を添加しペイントシェーカーで2時間分
散音行った後、脱イオン水800部をn1えて白色電着
塗料を調製した。
Ability to perform 2 Stirring % In a 3t flask equipped with a thermometer, commercially available acrylic thread polycarbonate side fat bath solution (product name Kota Sox WE152 manufactured by Toshisha Co., Ltd.) 85, mixed alkyl etherified methylol melamine (A-1 ) and 20 parts of Improvil alcohol were added and stirred at 30°C for 10 minutes, then n1 parts of deionized 7×40 parts were added and stirred for an additional 10 minutes. To this, 27 parts of titanium oxide (trade name: Kuibake CR-90, manufactured by Ishihara Sangyo Co., Ltd.) and 200 parts of glass beads were added, and after 2 hours of dispersion sound using a paint shaker, 800 parts of deionized water was added to form a white electrodeposition paint. Prepared.

比較fシリ2 実= yl12の方法において2混合アルキルエーテル
化メチロールメラミン樹脂を比較製造例1で調製したB
−126部と変えたり、外は、すべて向し方法を行い電
N塗料を調製した〇実施シリ6 かくはん機、温度計′(fl−備えた6tフラスコ中に
、市販のアクリル糸ポリカルボ/(社)樹霜浴液(商品
名 コータンクスWE152 3iし1ll)108部
、アルキンド樹脂(商品名 ウォーターゾルVS230
E1  大日本インキ社製)19都、混合アルキルエー
テル化メテロールメラミya(脂(A −2) 3 s
 HB、エチレングリコールモノブチルエーテル10部
及びトリエチルアミン1.5都を仕込み、50℃で30
分間かくはんを行い、ついで脱イオン水838都をカロ
えて希釈し電層塗料を調製した。
Comparative f sili 2 real = 2 mixed alkyl etherified methylol melamine resin prepared in Comparative Preparation Example 1 in the method of yl12 B
- 126 parts and all the other methods were used to prepare the electric N paint. 〇Execution Series 6 In a 6t flask equipped with a stirrer and a thermometer (fl-), a commercially available acrylic thread polycarbo ) 108 parts of frost bath liquid (product name: Cortanx WE152 3i 1ll), alkynd resin (product name: Watersol VS230)
E1 (manufactured by Dainippon Ink Co., Ltd.) 19, mixed alkyl etherified metherol melami ya (fat (A-2) 3 s
HB, 10 parts of ethylene glycol monobutyl ether, and 1.5 parts of triethylamine were charged, and the mixture was heated at 50°C for 30 minutes.
The mixture was stirred for a minute and then diluted with 838 g of deionized water to prepare an electrolayer paint.

比*9↑シリ 3 実施シリ5の方法において、混合アルキルエーテル化メ
チロールメラミン便脂全比較製造例1で調製したB−1
36都と変えた以外I′i、、すべて同し方法全行い電
層塗料を調製した。
Ratio*9↑Siri 3 Mixed alkyl etherified methylolmelamine stool sebum B-1 prepared in Comparative Production Example 1 in the method of Example 5
I'i. Electrolayer paints were prepared by following the same method except that the number was changed to 36.

実施P2す4 かくはん機、−度計を設えた3tフラスコ中に、市販の
アクリル系ポリカルボンW 樹脂電数(商品名 コーク
ツクスw E 152  末v社M )1089、?レ
イン化ポリブタジェン(商品名Nl5SO−PB  C
N1010  日本費達社H)20都、混合アルキルエ
ーテル化メチロールメラミン(A−11911x、エチ
レングリコールモノブチルエーテル20部及びジメテル
アミノエタノールム6部全仕込春、50℃に外扇して1
時間かくはんした後、脱イオン水815部をn1え希釈
し、ついでカーボンブランク分散液(商品名 工マコー
ルブンンク CN  LIJ陽色素社製少15部を冷加
しかくはん全行ない分散して黒色電層塗料全調製した。
Implementation P2-4 In a 3-ton flask equipped with a stirrer and a temperature meter, add commercially available acrylic polycarbonate resin (trade name: Coketux W E 152, manufactured by V Company M) 1089, ? Reinated polybutadiene (trade name Nl5SO-PBC
N1010 Nippon Kaidatsha H) 20 parts, mixed alkyl etherified methylol melamine (A-11911x, 20 parts of ethylene glycol monobutyl ether and 6 parts of dimethylaminoethanolam).
After stirring for an hour, 815 parts of deionized water was diluted to n1, and then 15 parts of a carbon blank dispersion (trade name: CN LIJ Yoshoku Co., Ltd., manufactured by Yoshoku Co., Ltd.) was cooled, stirred, and dispersed throughout the entire black electrolayer paint. Prepared.

比較例4 実施例4の方法において、混合アルキルエーテル化メチ
ロールメラミン樹脂を比較製造例1で調製したB−11
7部と変えた以外は、すべて同し方法全行い軍層塗料全
詞製した。
Comparative Example 4 In the method of Example 4, the mixed alkyl etherified methylol melamine resin B-11 prepared in Comparative Production Example 1
All the military layer paints were made using the same method except that the number 7 was changed.

電N塗装実験 実施例1〜4及び比較例1〜4で調製した電看塗料金用
いて、第2〜6表に示す条件で電層塗装全行い、塗膜全
120℃〜200℃で30分加熱乾燥し、その物理的性
質を測定した結果を第2〜6表に併記する。
Electron Coating Experiment Using the electrical paint gold prepared in Examples 1 to 4 and Comparative Examples 1 to 4, all electrical layer coating was carried out under the conditions shown in Tables 2 to 6. The results of measuring the physical properties are also shown in Tables 2 to 6.

ただし、電増塗装は、被塗物ケ陽極に、ステンレス板を
陰極に結線して行なった。被塗物として、陽極酸化アル
ミニウム(5)及びリン取鉄処理鋼板(均を1更川した
However, the electrostatic coating was carried out by connecting the object to be coated to the anode and the stainless steel plate to the cathode. The objects to be coated were anodized aluminum (5) and phosphorous-treated steel sheets (1 coat of aluminum).

塗膜性能は、JIS H−8602の方法に従って試験
した。ただし、耐浴剤性は、脱脂綿Vこメチルエテルケ
トン全し牟込壕せ、これで塗膜表面全こすり、塗膜に異
常が発生した回数金側ボした0又耐沸謄水性は耐那騰水
性試験故に光沢保持率を測定した。第2表〜第6衣は低
温焼付の効果を調食するために、120℃(第2表)、
140℃(第6表)、160℃(第4衣)、180℃(
第5表)及び200℃(第6表)で加熱乾燥して結果を
示す。
Coating film performance was tested according to the method of JIS H-8602. However, the bath agent resistance is determined by immersing absorbent cotton in a trench with methyl ether ketone, and rubbing the entire surface of the coating with it. Gloss retention was measured because of the water immersion test. The batters in Tables 2 to 6 were heated to 120℃ (Table 2) to adjust the effect of low-temperature baking.
140℃ (Table 6), 160℃ (No. 4 coating), 180℃ (
Table 5) and heat drying at 200°C (Table 6) and the results are shown.

〔発明の効果〕〔Effect of the invention〕

本発明の′屯庸塗1−4樹11i=組J戊物は、′電層
塗膜を佼化芒せる焼付温度を150℃未満1で下けるこ
とかでさ、かつホルマリンのヴ6生が抑制され又、焼句
炉の一度が低下でき省エネルギー、、低コスト化かり舵
となるという優れた効果全英する。
The main feature of the present invention is to lower the baking temperature to less than 150 degrees Celsius, and to reduce the temperature at which the electrolytic layer coating is cured to less than 150°C. It also has the excellent effect of suppressing the energy consumption of the burner and reducing energy consumption and cost reduction.

特許出願人  三井すイアナミント体式会社同   ハ
ニー化成株式会社
Patent applicant: Mitsui Suiana Mint System Company: Honey Kasei Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 1、(a)ポリカルボン酸樹脂50〜95重量部、及び
(b)メラミン核1個当り平均5個未満の結合ホルムア
ルデヒド、1.0〜3.5個のメチルエーテル基、0.
5〜3.0個のブチルエーテル基、0.5〜3.0個の
イミノ基、0.5個未満のメチロール基を有し、かつメ
ラミン核の平均重合度が1.5〜3.5である混合アル
キルエーテル化メチロールメラミン樹脂50〜5重量部
よりなることを特徴とする低温硬化型電着塗料樹脂組成
物。
1. (a) 50 to 95 parts by weight of polycarboxylic acid resin, and (b) an average of less than 5 bound formaldehyde per melamine nucleus, 1.0 to 3.5 methyl ether groups, 0.
It has 5 to 3.0 butyl ether groups, 0.5 to 3.0 imino groups, and less than 0.5 methylol groups, and the average degree of polymerization of the melamine core is 1.5 to 3.5. A low temperature curing electrodeposition coating resin composition comprising 50 to 5 parts by weight of a certain mixed alkyl etherified methylolmelamine resin.
JP63131584A 1988-05-31 1988-05-31 Low temperature curable electrodeposition coating resin composition Expired - Lifetime JP2543746B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63131584A JP2543746B2 (en) 1988-05-31 1988-05-31 Low temperature curable electrodeposition coating resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63131584A JP2543746B2 (en) 1988-05-31 1988-05-31 Low temperature curable electrodeposition coating resin composition

Publications (2)

Publication Number Publication Date
JPH01301768A true JPH01301768A (en) 1989-12-05
JP2543746B2 JP2543746B2 (en) 1996-10-16

Family

ID=15061472

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63131584A Expired - Lifetime JP2543746B2 (en) 1988-05-31 1988-05-31 Low temperature curable electrodeposition coating resin composition

Country Status (1)

Country Link
JP (1) JP2543746B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015141627A1 (en) * 2014-03-17 2015-09-24 日本ペイント・オートモーティブコーティングス株式会社 Aqueous coating composition, and coating film formation method
CN113088144A (en) * 2021-03-05 2021-07-09 广东呈美化学材料有限公司 Low-temperature curing water-based amino baking varnish coating applied to metal and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015141627A1 (en) * 2014-03-17 2015-09-24 日本ペイント・オートモーティブコーティングス株式会社 Aqueous coating composition, and coating film formation method
JP2015174958A (en) * 2014-03-17 2015-10-05 日本ペイント・オートモーティブコーティングス株式会社 Aqueous coating material composition and method for forming coating film
CN113088144A (en) * 2021-03-05 2021-07-09 广东呈美化学材料有限公司 Low-temperature curing water-based amino baking varnish coating applied to metal and preparation method thereof

Also Published As

Publication number Publication date
JP2543746B2 (en) 1996-10-16

Similar Documents

Publication Publication Date Title
AU2010208363B2 (en) Electrodepositable coating composition comprising silane and yttrium
CN101302642A (en) Method for forming electrodeposition coating
CN1156543C (en) Cathodic electrocoating compositions containing anticrater agent
JPH0739558B2 (en) Resin composition for organic solvent type paint
EP0214599B1 (en) Composition for electrodeposition paint
US3960688A (en) Process for electrodepositing coatings on metal
JPH01301768A (en) Low-temperature curing type electrodeposition coating resin composition
EP2414465A1 (en) Electrocoating composition comprising a crater control additive
WO1985001506A1 (en) Self-curing resin composition
JPS6114268A (en) Paint material and manufacture
US20110214992A1 (en) Electrodepositable coating composition comprising a bismuth salt and a stabilizing compound
CA2805193C (en) Copper prerinse for electrodepositable coating composition comprising yttrium
JPH01121369A (en) Coating resin composition
JPH0337274A (en) Aqueous solution or dispersion of vehicle for water-base coating material
JPH04339870A (en) Low-temperature curing electrodeposition coating resin composition
CN105705545A (en) Cationic alkyd resins
US6174965B1 (en) Polyester resin, process for its production and its use
JPH03500056A (en) Process for the preparation of cathodically depositable aqueous dispersions containing crosslinking agents based on polyisocyanates blocked with hydroxyl groups
JP2794298B2 (en) Thermosetting coating composition
JPH0131792B2 (en)
JPS62236873A (en) Electrodeposition coating composition
JP3337485B2 (en) Thermosetting water-dispersed resin composition and coating composition
JPH0132266B2 (en)
JPH02142815A (en) Production of mixed alkyl-etherified methylolmelamine resin
JPS63268775A (en) Matte electrodeposition coating composition

Legal Events

Date Code Title Description
EXPY Cancellation because of completion of term