JPS60186524A - Intermediate coating composition for automobile - Google Patents
Intermediate coating composition for automobileInfo
- Publication number
- JPS60186524A JPS60186524A JP4143084A JP4143084A JPS60186524A JP S60186524 A JPS60186524 A JP S60186524A JP 4143084 A JP4143084 A JP 4143084A JP 4143084 A JP4143084 A JP 4143084A JP S60186524 A JPS60186524 A JP S60186524A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin
- caprolactone
- parts
- bisphenol
- 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
Abstract
Description
【発明の詳細な説明】
本発明は、自動車用中塗り塗料組成物に関するものであ
る。詳しくはすぐれた耐ストーンチッピング性を有する
、車体防錆保獲を目的とした自動車用中塗り塗料組成物
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an intermediate coating composition for automobiles. More specifically, the present invention relates to an automotive intermediate coating composition that has excellent stone chipping resistance and is intended to protect car bodies from rust.
自動車外板には、一般に鋼板の上に前処理として化成処
、Ｉｌｌ！（リン酸亜鉛処理など）を施し、次いで下塗
り塗料（電着塗料）を塗装し焼き付は後、中塗り塗料を
塗装し焼き付け、次いで上塗り塗料を塗装し焼き付けて
積層膜を形成させ、美粧を兼ねた防錆塗膜処理が成され
ている。For automobile exterior panels, a chemical treatment is generally applied to the steel plate as a pre-treatment. (zinc phosphate treatment, etc.), then apply an undercoat (electrodeposition paint) and bake it, then apply an intermediate coat and bake it, then apply a topcoat and bake it to form a laminated film to create a beautiful makeup. It has been treated with a rust-preventing coating that also serves as an anti-rust coating.
１−かし自動車外板は、車輛の走行時に路面上の石など
をはね上げて車体に当接する、いわゆるストーンチッピ
ング現象によって、上記塗膜が損傷し、金属が露出して
発錆、腐食するため、従来からストーンチッピング耐性
を有する塗膜を形成する方法が提案されている。1- The so-called stone chipping phenomenon, in which stones and other objects on the road surface are thrown up and hit the car body when the car is running, damages the paint film and exposes the metal, causing rust and corrosion. Conventionally, methods for forming coating films having resistance to stone chipping have been proposed.
それらの対策の１つとして、中塗り塗膜に無・機偏平顔
料たとえば、タルク、絹雲母などを含有せしめ、ストー
ンチッピングの際塗膜内部に凝集破壊を生じさせる耐ス
トーンチッピング性中塗シ塗料が、たとえば特公昭５２
−４３６５７号、特公昭５３−４５８１３号、特開昭５
５−５６１６５号、特公昭５６−１６７７６４号などで
提案されている。One of the countermeasures is to create a stone chipping resistant intermediate coating that contains inorganic flat pigments such as talc and sericite in the intermediate coating to cause cohesive failure within the coating during stone chipping. , for example, the special public service of 1972
-43657, Japanese Patent Publication No. 53-45813, Japanese Patent Publication No. 53-45813
This method has been proposed in Japanese Patent Publication No. 5-56165 and Japanese Patent Publication No. 56-167764.
しかし、これらの無機偏平顔料を混入する方法は、その
含有量が多い場合にはスト−ンチッピングの際、凝集破
壊能はある。が塗膜はく離を生ずる面積が大きくなシ、
美観を損ねる傾向があり、また、その含有量が少ない場
合には凝集破壊能が劣シ、金属の露出による発錆を生ず
る傾向がある。However, in the method of mixing these inorganic flat pigments, if the content is large, there is a possibility of cohesive failure during stone chipping. If the area where paint peels off is large,
It tends to impair the aesthetic appearance, and if its content is low, it has poor cohesive failure ability and tends to cause rust due to metal exposure.
また別の対策として、上塗りあるいは電着塗膜との付着
性を向上させ、ストーンチッピング時の上塗シと中塗り
間、あるいは中塗シと電着塗膜間の界面はく離を防止し
、はく離による美観損失を防止する目的で、ビスフェノ
ール形エポキシ樹脂を中塗り塗料に使用する方法がある
。Another measure is to improve the adhesion with the top coat or electrodeposition coating, and prevent peeling at the interface between the topcoat and the intermediate coat, or between the intermediate coat and the electrodeposition coating during stone chipping, and improve the aesthetic appearance due to peeling. For the purpose of preventing loss, there is a method of using bisphenol type epoxy resin as an intermediate coating.
しか［７、通常中塗り塗料に用いられるポリエステル・
メラミン樹脂併用の樹脂成分系においては、加えられる
このビスフェノール形エポキシ樹脂は、水酸基が反応性
の低い２級であるため硬化反応にあずからず、単にブレ
ンドされているにすぎない。However [7, polyester usually used in intermediate coatings]
In a resin component system in which melamine resin is used in combination, the bisphenol type epoxy resin added has a secondary hydroxyl group with low reactivity, so it does not participate in the curing reaction and is simply blended.
従って、ブレンド量が多い場合は上塗りと中塗り間、あ
るいは中塗りと電着塗膜間の界面はく離が防止でき、層
間での破壊面積は小さくできるが、一方、中塗り塗膜の
凝集力が不足し、中塗り塗膜層間での凝集破壊傾向が生
じ、ストーンチッピング時の中塗り層内でのはく離面積
が大きくなる傾向がある。寸だ、ビスフェノール形エポ
キシ樹脂は硬度が高いため、塗膜硬度が増加し、可とう
性が低くなる欠点がある。Therefore, when the amount of blending is large, interfacial peeling between the top coat and the intermediate coat or between the intermediate coat and the electrodeposition coating can be prevented, and the area of failure between the layers can be reduced, but on the other hand, the cohesive force of the intermediate coat can be reduced. If the amount is insufficient, cohesive failure tends to occur between the intermediate coating layers, and the peeling area within the intermediate coating layer during stone chipping tends to increase. However, since bisphenol-type epoxy resins have high hardness, they have the disadvantage of increasing coating hardness and decreasing flexibility.
本発明者らは、このようなビスフェノール形エボキ７樹
脂の、メラミン樹脂との反応性や可とう性に関する欠点
を排除し、ビスフェノール形エポキシ樹脂の長所である
付着性を損なわない使用方法について鋭意研究した結果
、ビスフェノール形エポキシ樹脂の水酸基に、ε−カプ
ロラクトンをグラフト重合させることにより改良され、
塗膜仕上り外観性ならびに耐ストーンチッピング性に優
れた中塗シ塗料が得られることを見出し２、本発明をな
すに至ったものである。The present inventors have conducted extensive research on a method of using bisphenol-type epoxy resin that eliminates the disadvantages of reactivity with melamine resin and flexibility, and does not impair the adhesion properties that are the advantages of bisphenol-type epoxy resin. As a result, it was improved by graft polymerizing ε-caprolactone to the hydroxyl group of bisphenol type epoxy resin.
It was discovered that an intermediate coating material having excellent finish appearance and stone chipping resistance can be obtained2, and the present invention was developed.
すなわち、本発明は、塗膜形成成分となる樹脂成分中に
、ビスフェノール形エポキシ樹脂の水酸基に、ε−カプ
ロラクトンをグラフト重合させた樹脂を含有することを
特徴とする自動車用中塗り塗料組成物に関するものであ
る。That is, the present invention relates to an intermediate coating composition for automobiles, characterized in that the resin component serving as a coating film forming component contains a resin obtained by graft polymerizing ε-caprolactone to the hydroxyl group of a bisphenol type epoxy resin. It is something.
本発明の中塗り塗料組成物に用いる、ビスフェノール形
エポキシ樹脂の水酸基にε−カプロラクトンをグラフト
重合させた樹脂は、次のようにして構造する。The resin used in the intermediate coating composition of the present invention, in which ε-caprolactone is graft-polymerized to the hydroxyl group of a bisphenol type epoxy resin, has the structure as follows.
すなわち、ビスフェノール形エポキシＩｆ 脂’ｄ、ビ
スフェノールＡとエピクロールヒドリンとの反応によっ
て得られる、次のような構造を有するジグリシジルエー
テルエポキシ樹脂であって、この樹脂に、テトラブチル
チタネート、テトラプロピルチタネート、テトラエチル
チタネートなどのチタン化合物、オクチル酸スズ、ジブ
チルスズオキシド、ジブチルスズジラウレートなどの有
機スズ化合物を触媒とし、８−カプロラクトンを既知の
方法（例えば特開昭５８−３２６２８号などに記載され
た方法）Ｋよってグラフト重合させ、以下のような構造
のビスフェノール形エポキシ樹脂のε−力プロ２クトン
クラフト重合物とする。That is, it is a diglycidyl ether epoxy resin having the following structure obtained by the reaction of bisphenol type epoxy If fat, bisphenol A and epichlorohydrin, and this resin is added with tetrabutyl titanate, tetrapropyl A titanium compound such as titanate or tetraethyl titanate, an organic tin compound such as tin octylate, dibutyltin oxide, or dibutyltin dilaurate is used as a catalyst, and 8-caprolactone is used in a known method (for example, the method described in JP-A-58-32628). Graft polymerization is performed using K to obtain an ε-force pro2 chthon craft polymer of bisphenol type epoxy resin having the following structure.
使用されるビスフェノール型エポキシ樹脂ハ、エポキシ
当量が２００〜７０００の範囲のものであり、好ましく
は４００〜３０００の範囲のものである。エポキシ当量
が２００未満では中塗シ塗膜の硬度が十分ではなく、７
０００を超える場合は他の樹脂との相容性が不良となる
。また、ｇ−カプロラクトンの付加モル数は、ビスフェ
ノール形エポキシ樹脂の水酸基１モルに対し、平均０．
５〜１．０モルが好ましく、０゜５モル未満の場合は中
塗り塗膜の硬化性と可とう性が不十分とな、！Ｄ、、１
．０モルを超える場合は中塗シ塗膜の硬度が不足となる
。The bisphenol type epoxy resin used has an epoxy equivalent of 200 to 7,000, preferably 400 to 3,000. If the epoxy equivalent is less than 200, the hardness of the intermediate coating film will not be sufficient;
If it exceeds 000, compatibility with other resins will be poor. Furthermore, the number of moles of g-caprolactone added is on average 0.00% per mole of hydroxyl group of the bisphenol type epoxy resin.
5 to 1.0 mol is preferable, and if it is less than 0.5 mol, the curability and flexibility of the intermediate coating film will be insufficient! D,,1
．． If the amount exceeds 0 mol, the hardness of the intermediate coating film will be insufficient.
本発明による中塗り塗料組成物は、このビスフェノール
形エポキシ樹脂の２級の水酸基にε−カプロラクトンを
グラフト重合させることにより、末端が１級の水酸基を
もつビスフェノール形エポキシ樹脂となり、これによっ
てメラミン樹脂との反応性が玩＃巷≠改善され、塗膜の
凝集力を高め、ストーンチッピング時のはぐり程度や素
地到達傷の発生を減少させる。また、このε−カプロラ
クトンで変性したエポキシ樹脂は、グリシジル基をその
１ま含有するため、エポキシ樹脂を含有するカチオン電
着下塗り膜との付着性はもとのエポキシ樹脂と同等であ
り、またメラミン樹脂との反応性向上によシ、上塗シ塗
膜のようなメラミン樹脂含有塗膜との間の付着性が向丘
する。さらに、通常のビスフェノール形エポキシ樹脂を
多量ニフレンドした場合は、可とう性が劣るが、ε−カ
プロラクトン変性ビスフェノール型エポキシ樹脂は、ε
−カプロラクトン部分の可塑化効果により可とう性が低
下しない。The intermediate coating composition according to the present invention becomes a bisphenol epoxy resin having a primary hydroxyl group at the terminal by graft polymerizing ε-caprolactone onto the secondary hydroxyl group of this bisphenol epoxy resin, and thereby becomes a bisphenol epoxy resin with a primary hydroxyl group. This improves the reactivity of the coating, increases the cohesive force of the paint film, and reduces the degree of chipping during stone chipping and the occurrence of scratches that reach the substrate. In addition, since the epoxy resin modified with ε-caprolactone contains at least one glycidyl group, its adhesion with the cationic electrodeposited undercoat film containing the epoxy resin is the same as that of the original epoxy resin, and the melamine By improving the reactivity with the resin, the adhesion with melamine resin-containing coatings such as top coats improves. Furthermore, when a large amount of ordinary bisphenol-type epoxy resin is nifriended, the flexibility is inferior, but ε-caprolactone-modified bisphenol-type epoxy resin has ε
- Flexibility does not decrease due to the plasticizing effect of the caprolactone moiety.
このε−カプロラクトン変性ビスフェノール型エポキシ
樹脂は、塗料の樹脂成分１００重１中１〜５０重量部を
用いるが好ましくは５〜４０重量部が適当である。１重
量部未満では塗膜層間の付着性が不十分であり、５０重
量部を越える場合は塗膜外観が劣る様になる。The ε-caprolactone-modified bisphenol epoxy resin is used in an amount of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the resin component of the paint. If it is less than 1 part by weight, the adhesion between the coating layers will be insufficient, and if it exceeds 50 parts by weight, the appearance of the coating will be poor.
ε−カプロラクトン変性ビスフェノール型エポキシ樹脂
と併用するメラミン樹脂は、ブトキシメチロールメラミ
ン樹脂、イソブトキシメチロール−４０重量部好ましく
は２０〜３０重量部の使用が適当である。１０重量部未
満では塗膜の硬化性が不十分であり、４０重量部を越え
る可とう性が劣る。The melamine resin used in combination with the ε-caprolactone-modified bisphenol epoxy resin is suitably a butoxymethylol melamine resin or isobutoxymethylol in an amount of 40 parts by weight, preferably 20 to 30 parts by weight. If the amount is less than 10 parts by weight, the curability of the coating film will be insufficient, and if it exceeds 40 parts by weight, the flexibility will be poor.
１だ上記２樹脂酸分と併用するポリエステル樹脂として
は、グリセリン、ペンタエリスリトール、ジプロピレン
グリコールなどのポリオールと無水フタル酸、イソフタ
ル酸、アジピン酸、セバシン酸などの多塩基酸成分およ
び脂肪酸、安息香酸、ターシャリ−ブチル安息香酸など
の１塩基酸成分９〜
の縮重合物寮弁社命、いわゆるポリエステル樹脂であっ
て、塗料組成物の樹脂成分１００重量部中３０〜７０重
量部を用いるが、好ましくは３５〜６５重量部が適当で
ある。３０重量部末端では塗膜外観が劣り、、７０重計
部を越えると塗膜の層間付着性が不十分となる。Polyester resins used in combination with the above two resin acid components include polyols such as glycerin, pentaerythritol, and dipropylene glycol, polybasic acid components such as phthalic anhydride, isophthalic acid, adipic acid, and sebacic acid, fatty acids, and benzoic acid. , a condensation polymer of 9 to 90% of a monobasic acid component such as tert-butylbenzoic acid, a so-called polyester resin, preferably used in an amount of 30 to 70 parts by weight in 100 parts by weight of the resin component of the coating composition. A suitable amount is 35 to 65 parts by weight. At the end of 30 parts by weight, the appearance of the coating film is poor, and when it exceeds 70 parts by weight, the interlayer adhesion of the coating film becomes insufficient.
この他塗料組成物中の樹脂成分として、アクリル樹脂、
エポキシ樹脂、繊維素系樹脂なども併用することができ
る。Other resin components in the paint composition include acrylic resin,
Epoxy resins, cellulose resins, etc. can also be used in combination.
これら塗料組成物中の樹脂成分は、従来中塗り塗料に用
いられるのと同隊に３０〜７００〜７０重量部れる。The resin components in these coating compositions are in the same range of 30 to 700 to 70 parts by weight as those conventionally used in intermediate coatings.
本発明の中塗シ塗料組成物には、顔料としてタルク、二
酸化チタン、亜鉛華、酸化鉄、カーボンブランク、硫酸
バリウム、カオリン、炭酸カルシウム、絹雲母、板状硫
酸バリウム、トリポリリン酸アルミニウム、リンモリブ
デン酸亜鉛アルミニウム、−塩基性硫酸鉛などを従来の
中塗シ塗料の場合と全く同様に３０〜７０重量％使用す
ることができるが、就中タルクは塗膜内部に凝集破壊を
生じさせて耐ストンチッピング性を与えるため、中塗シ
塗料組成物中１〜２重量％（樹脂成分に対し約２〜４重
量％）を用いることが好ましい。しかし使用量が２重量
楚を超える場合は、ストーンチッピング時のはく離を生
ずる面積が大きくなり、１重量％未満の場合は衝撃緩和
力がやや不十分である。The intermediate coating composition of the present invention contains talc, titanium dioxide, zinc white, iron oxide, carbon blank, barium sulfate, kaolin, calcium carbonate, sericite, tabular barium sulfate, aluminum tripolyphosphate, and phosphomolybdic acid as pigments. Zinc aluminum, basic lead sulfate, etc. can be used in an amount of 30 to 70% by weight, just as in the case of conventional intermediate coatings, but talc in particular causes cohesive failure within the coating film to prevent stone chipping. It is preferable to use 1 to 2% by weight (approximately 2 to 4% by weight based on the resin component) of the intermediate coating composition in order to impart properties. However, if the amount used exceeds 2% by weight, the area where delamination occurs during stone chipping becomes large, and if the amount is less than 1% by weight, the impact mitigation power is somewhat insufficient.
本発明の中塗り塗料組成物には、さらに必要によシキン
レン、トルエン、ツルペッツ≠１００（商品名、エクソ
ン社製）、酢酸ブチルエステル、メチルイソブチルケト
ン、酢酸エチレングリコールモノエチルエーテルなどの
溶剤や添加剤を用いることができる。The intermediate coating composition of the present invention may further contain solvents and additives such as toluene, toluene, Trupetz≠100 (trade name, manufactured by Exxon), butyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate. Agents can be used.
本発明の中塗り塗料組成物は、従来の自動車用中塗貞）
塗料甜成物の製造方法と同様な手法によって製造するこ
とができる。すなわち、顔料と樹脂フェス（樹脂溶液）
とを混合し、ボールミルやロールミルで分散させ、その
後適宜、樹脂フェス、溶剤および添加剤を加え、均一に
かくはんして中塗シ塗料組成物とする。The intermediate coating composition of the present invention is a conventional intermediate coating composition for automobiles.
It can be manufactured by a method similar to that used for manufacturing paint products. i.e. pigment and resin face (resin solution)
The mixture is mixed and dispersed using a ball mill or roll mill, and then a resin face, a solvent, and additives are added as appropriate, and the mixture is uniformly stirred to obtain an intermediate coating composition.
本発明の中塗り塗料組成物は、通常、電着下塗り塗膜を
形成させた鋼板に、従来の中塗り塗料と同様ニエアース
プレー、エアレススプレー、空気霧化式静電塗装、回転
霧化式静電塗装などの塗装方法によって、塗膜厚２０〜
６０ミクロン好ましくは３５〜４５ミクロン塗装される
。塗膜厚が２０ミクロン未渦の場合はストーンチッピン
グ防止能が劣り、６０ミクロンを越える場合は面１屈曲
性などが低下する。The intermediate coating composition of the present invention is usually applied to a steel plate on which an electrodeposition undercoat film has been formed, in the same way as conventional intermediate coatings, such as near-air spray, airless spray, air atomization electrostatic coating, or rotary atomization coating. Depending on the coating method such as electrostatic coating, the coating thickness is 20~
60 microns preferably 35-45 microns coated. If the coating thickness is 20 microns or less, the ability to prevent stone chipping will be poor, and if it exceeds 60 microns, surface 1 flexibility will be reduced.
本発明の中塗り塗料組成物は、電着下塗り塗膜上に１コ
ート塗装し、焼付け、さらにその上に上塗り塗膜を形成
させる方法が一般的な塗装仕様であるが、中塗り塗膜を
形成後、焼付けずにまたは焼付は後、耐ストーンチッピ
ング性を持たない別の中塗り塗料を塗装して焼付ける、
中塗シ塗料の２コート塗装系に代えてもその耐スＩ・−
ンチソビング性は影響を受けず効果がある。この様に塗
装方式をいろいろに代えても、その耐ストーンチツピン
グ性能は変らない特徴がある。The intermediate coating composition of the present invention is generally applied by applying one coat on an electrodeposited undercoat film, baking it, and then forming a topcoat film thereon. After forming, without baking or after baking, apply another intermediate coating that does not have stone chipping resistance and bake.
Even if you replace it with a two-coat intermediate paint system, its scratch resistance is still high.
antisobbing properties are unaffected and effective. As described above, even if the coating method is changed, the stone chipping resistance remains the same.
以上述べたように、本発明による自動車用中塗シ塗料組
成物は、可とう性が優れ、塗膜の凝集力が強く、塗膜層
間の付着性が高いことから、塗膜仕上り外観ならびに耐
ストーンチッピング性に優れた中塗シ塗膜を得ることが
できる。As described above, the intermediate coating composition for automobiles according to the present invention has excellent flexibility, strong cohesive force of the coating film, and high adhesion between the coating layers, which improves the appearance of the coating film and its stone resistance. An intermediate coating film with excellent chipping properties can be obtained.
つぎに本発明の実施例、比較例をあげて本発明をさらに
詳細に説明する。例中、部は重量部、飴は重量部である
。Next, the present invention will be explained in more detail by giving Examples and Comparative Examples of the present invention. In the examples, parts are parts by weight, and candy is parts by weight.
ε−カプロラクトン変性ビスフェノール型エポキシ樹脂
ワニスの調製
（ａ）ε−カプロラクトン変性ビスフェノール形エポキ
シ樹脂ワニスＡ
ビスフェノールＡとエピクロールヒドリンとから合成さ
れたビスフェノール形エポキシ樹脂〔チバガイギー社製
、商品名アラルダイトＧＹ６０７１（エポキシ当量４５
０〜５００．融点６４〜７４℃）１９００部、ε−カプ
ロラクトン１００部およびテトラブチルチタネートｏ、
ｏｘｓを２ｔガラスフラスコに入れ、窒素ガスを吹き込
みながら１７０〜１８０℃で７時間かくはんした。得ら
れたε−カプロラクトン変性ビスフェノール形エポキシ
樹脂Ａは、融点３５℃、エポキシ当量５５０、ε−カプ
ロラクトン平均付加モルａＯ１８モル１０Ｈであった。Preparation of ε-caprolactone modified bisphenol epoxy resin varnish (a) ε-caprolactone modified bisphenol epoxy resin varnish A Bisphenol epoxy resin synthesized from bisphenol A and epichlorohydrin [manufactured by Ciba Geigy, trade name Araldite GY6071] Epoxy equivalent 45
0~500. melting point 64-74°C) 1900 parts, ε-caprolactone 100 parts and tetrabutyl titanate o,
Oxs was placed in a 2t glass flask and stirred at 170 to 180°C for 7 hours while blowing nitrogen gas. The obtained ε-caprolactone-modified bisphenol epoxy resin A had a melting point of 35° C., an epoxy equivalent of 550, and an average addition mole of ε-caprolactone of 18 mols of ε-caprolactone.
この樹脂Ａにキシレン３３３部および酢ａ工ｆｖ／ｙ＋
）コールモノエチルニーフル３３３都加え、不揮発分６
０％のε−カプロラクトン変性ビスフェノール形エポキ
シ樹脂フェスＡを得た。To this resin A, 333 parts of xylene and vinegar a
) Coal monoethyl needle 333 plus non-volatile content 6
A 0% ε-caprolactone modified bisphenol type epoxy resin face A was obtained.
（ｂ）ε−カプロラクトン変性ビスフェノール形エポキ
シ樹脂ワニスＢ
ビスフェノールＡとエピクロールヒドリントカら合成さ
れたビスフェノール形エポキシ樹脂〔油化シエルエポキ
シ１掬製、商品名工ピコ−トナ１００７（エポキシ当量
准１７５０〜２１００．１独点１２２〜１３１℃））Ｓ
ＯＯ部、ε−カプロラクトン２００部およびテトラプチ
ルテタネー＋−ｏ、 ｏ ｉ部を２ｔガラスフラスコに
入れ、窒素ガスを吹き込みながら前記エポキシ樹脂Ａと
同一の方法で合成した。得られたε−カプロラクトン変
性エポキシ樹脂は、融点６３℃、エポキシ当量３８００
、ε−カプロラクトン平均付加モル数０．７モル１０Ｈ
であった。この樹脂にキシレン３３３部、および酢酸エ
チレングリコールモノエチルエーテル３３３部／ＪＤえ
、不揮発分６０％のε−カプロラクトン変注ビスフェノ
ール形エポキ７樹脂ワニスＪ３を得た。(b) ε-caprolactone modified bisphenol type epoxy resin varnish B Bisphenol type epoxy resin synthesized from bisphenol A and epichlorhydrinol [manufactured by Yuka Ciel Epoxy 1 scoop, trade name Ko Pico Tona 1007 (epoxy equivalent: 1750-2100) .1 independent point 122-131℃))S
Part OO, 200 parts of ε-caprolactone, and parts of tetrabutyl tetane+-o, oi were placed in a 2-t glass flask, and synthesized in the same manner as the epoxy resin A while blowing nitrogen gas. The obtained ε-caprolactone modified epoxy resin had a melting point of 63°C and an epoxy equivalent of 3800.
, ε-caprolactone average number of moles added 0.7 moles 10H
Met. To this resin, 333 parts of xylene and 333 parts of ethylene glycol monoethyl ether acetate/JD were added to obtain ε-caprolactone modified bisphenol type epoxy 7 resin varnish J3 having a non-volatile content of 60%.
ポリエステル樹脂ワニスの調製
（ａ）ポリエステル樹脂ワニスＡ
グリセリン４．３部、ネオペンチルグリコール２０．２
部、アシヒン酸１４．３部およびイソフタル酸２４．４
部を２３０℃で６時間エステル化反応させ、冷却後キシ
レンとメチルイソブチルケトンとの等重量混合溶剤３０
．８部を加え、固形分６０％のポリエステル樹脂ワニス
Ａを得た。Preparation of polyester resin varnish (a) Polyester resin varnish A 4.3 parts of glycerin, 20.2 parts of neopentyl glycol
parts, 14.3 parts of acyhinic acid and 24.4 parts of isophthalic acid.
The mixture was subjected to an esterification reaction at 230°C for 6 hours, and after cooling, a mixed solvent of equal weights of xylene and methyl isobutyl ketone (30%) was added.
．． 8 parts were added to obtain polyester resin varnish A having a solid content of 60%.
（ｂ）ポリエステル樹脂ワニスＢ
トリメチロールプロパン２３．２ ｔｓ、アジピン酸８
９部、イソフタル酸１４．８部および大豆油脂肪酸１９
．１部を２３０℃で６時間エステル化反応させ、冷却後
キシレンとメチルイソブチルケトンとの等重量混合溶剤
３４部′を加えて、固形分６゜チのポリエステル樹脂ワ
ニスＢを得た。(b) Polyester resin varnish B trimethylolpropane 23.2 ts, adipic acid 8
9 parts, isophthalic acid 14.8 parts and soybean oil fatty acid 19 parts
．． One part was subjected to an esterification reaction at 230°C for 6 hours, and after cooling, 34 parts of a mixed solvent of equal weight of xylene and methyl isobutyl ketone was added to obtain polyester resin varnish B with a solid content of 6°C.
実施例１〜６、比較例１〜４
第１表に示す実施例および比較例の配合組成物それぞれ
を、ボットミルで十分混練し、実施例１〜６、比較例１
〜４の中塗シ塗料組成物を得た。Examples 1 to 6, Comparative Examples 1 to 4 The blended compositions of Examples and Comparative Examples shown in Table 1 were thoroughly kneaded using a bot mill, and Examples 1 to 6 and Comparative Example 1 were obtained.
-4 intermediate coating paint compositions were obtained.
＊１．二酸化チタン、帝国化工■製、商品名Ｊ’Ｒ−６
０２
＊２ 微粉タルク：富士タルク工業■製、商品名タルク
ＭＴ−６Ｂ（５０％平均粒径１．４ミクロン）
＊３８ カーボンブラック：コロンビアカーボン社製、
商品名ラーベン４２０
＊４．硫酸バリウム：堺化学■襄、商品泡洗バリ５Ｓ−
５０
＊５ エポキシ樹脂ワニスＣ：チバガイギー社製、商品
名アラルダイトＧＹ−１３０７１，６０％溶液
＊６ エポキシ崩脂ワニスＤ：？ｌｉｌ化シェルエポキ
シ■製、商品名工ピコ−）１００７．６０係溶液
＊７ イソブチル化メラミン樹脂フェス１日本うイヒホ
ールド■製、商品名スーパーペラ−ストマン社製、商品
名セルロースアセテートプチレー）ＣＡＢ３８１−０．
５．２０俤溶液
得られた実施例、比較例の中塗シ塗料組成物を、芳香族
溶剤（ツルペッツ−４１００、商品名、エクソン社・Ｍ
）と酢ばブチルエステルの等重量混合溶剤を用いて、そ
れぞれ粘度を２３秒（フォードカップ≠４、温度２０℃
）に調整し、大きさ０．８×ＩＱＯＸ１５０諭のダル鋼
板にリン酸亜鉛処理（日本パーカライジング■製、商品
名ボンデライトナ３００４処理）した後カテオ／電着塗
料（日本油ｌｌ”＆＠製、商品名アクアＮＣＬ４１００
）を塗装し、１６５℃で３０分間焼き付けた上に乾燥塗
膜厚として４０ミクロンとなるごとくエアースプレー塗
装し、１４０℃で３０分間焼き付け１．続いて上塗りと
してアミノアルキド樹脂塗料（日本油脂■製、商品名メ
ラミンＮ（１１ホワイト）をスプレー塗装し、１４０℃
で３０分間焼き付けた。乾燥後の上塗り膜厚は３８〜４
２ミクロンであった。調製した試験片について、下記に
示す試験条件のストーンチノビ／グチストとツルトスプ
レーテストを行なった。この結果を第２表に示す。*1. Titanium dioxide, manufactured by Teikoku Kako ■, product name J'R-6
02 *2 Fine powder talc: manufactured by Fuji Talc Industries ■, trade name Talc MT-6B (50% average particle size 1.4 microns) *38 Carbon black: manufactured by Columbia Carbon Company,
Product name Raven 420 *4. Barium sulfate: Sakai Chemical Co., Ltd., product foam washing bari 5S-
50 *5 Epoxy resin varnish C: Ciba Geigy, trade name Araldite GY-13071, 60% solution *6 Epoxy fat-soluble varnish D: ? Made by Lillized Shell Epoxy (trade name: Pico) 1007.60 solution*7 Isobutylated melamine resin Fes 1 Made by Nippon Uichhold (trade name: Super Perastman Co., trade name: Cellulose Acetate Petite) CAB381-0 ．．
5. The intermediate coating compositions of the Examples and Comparative Examples obtained in the 20-year solution were mixed with an aromatic solvent (Turupetz-4100, trade name, Exxon Co., Ltd., M
) and vinegar butyl ester in an equal weight mixed solvent, the viscosity was adjusted to 23 seconds (Ford cup≠4, temperature 20℃).
), and a dull steel plate with a size of 0.8 x IQOX150 was treated with zinc phosphate (manufactured by Nippon Parkerizing ■, product name: Bonderitetona 3004 treatment), and then cateo/electrodeposition paint (manufactured by Nippon Oil & Co., Ltd., product name) was applied. Name Aqua NCL4100
) and baked at 165°C for 30 minutes, then air sprayed to a dry coating thickness of 40 microns and baked at 140°C for 30 minutes 1. Next, as a top coat, amino alkyd resin paint (manufactured by NOF ■, trade name Melamine N (11 White)) was spray-painted and heated at 140°C.
Bake for 30 minutes. Top coat thickness after drying is 38-4
It was 2 microns. The prepared test pieces were subjected to Stonechinovi/Gutist and Tsuruto spray tests under the test conditions shown below. The results are shown in Table 2.
４第２表 試験結果 ストーンチッピングテストの条件は下記に従った。4 Table 2 Test results The conditions for the stone chipping test were as follows.
試験機：スガ試験機掬製グラベロメーター試験石ニア号
硬質砂岩砕石（２〜：３＋ｍｎ１ｌｌ）１回１００１
吹き付は空気圧： ３ Ｖ４／ ｃｒｌ吹き付は角度＋
９０’
試験片温度：２０℃
ストーンチッピング塗膜はく離評価は次の基準に従った
。Testing machine: Suga Test Instruments Kiki Gravelometer Test Stone Nia No. Hard Sandstone Crushed Stone (2~:3+mn1ll) 1 time 1001 Air pressure for spraying: 3 V4/crl Spraying angle +
90' Test piece temperature: 20°C Stone chipping coating peeling evaluation was based on the following criteria.
はく離径０．５ ｗｎ未満のもの ○（憂）はく離径０
５閣を超えるもの ×（劣）また、発錆評価は上記試験
片をノルドスプレー（温度３５℃、５％塩水噴霧）２４
０時間後の発情点数を数え以下の基準で分離した。Peeling diameter less than 0.5 wn ○(Concern) Peeling diameter 0
Those exceeding 5 degrees × (poor) In addition, for the rust development evaluation, the above test piece was subjected to Nord spray (temperature 35°C, 5% salt water spray) 24
The number of estrous points after 0 hours was counted and separated according to the following criteria.
３０個所未満の発端 Ｏ（祷）
３０個所を超える７０個所未満の発錆 △（可）７０個
所を超える発錆 ×（劣）
・！ｇ２表から明らかなように、実施例１〜６は、比較
例１〜４に比べてストーンチッピング塗膜のはく離評価
に優れ、ツルトスプレーテストの発錆の評価のうえでも
優れていることがわかる。Origin of rust in less than 30 places O (prayer) Rust in more than 30 places but less than 70 places △ (Acceptable) Rust in more than 70 places × (Poor) ・! As is clear from the g2 table, Examples 1 to 6 are superior to Comparative Examples 1 to 4 in peeling evaluation of the stone chipping coating, and are also superior in evaluation of rusting in the Tsuruto spray test. .
特許出願人 日本油脂株式会社Patent applicant: NOF Corporation
Claims (1)
ポキシ樹脂の水酸基に、ε−カプロラクト／をグラフト
重合させた樹脂を含有することを特徴とする自動車用中
塗シ塗料組成物。An intermediate coating composition for automobiles, characterized in that a resin component serving as a coating film-forming component contains a resin obtained by graft polymerizing ε-caprolact onto the hydroxyl groups of a bisphenol type epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4143084A JPS60186524A (en) | 1984-03-06 | 1984-03-06 | Intermediate coating composition for automobile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4143084A JPS60186524A (en) | 1984-03-06 | 1984-03-06 | Intermediate coating composition for automobile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60186524A true JPS60186524A (en) | 1985-09-24 |
Family
ID=12608148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4143084A Pending JPS60186524A (en) | 1984-03-06 | 1984-03-06 | Intermediate coating composition for automobile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60186524A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62164738A (en) * | 1986-01-14 | 1987-07-21 | Kansai Paint Co Ltd | Paint composition for polyurethane resin molding |
| US5126413A (en) * | 1988-09-29 | 1992-06-30 | Kansai Paint Co., Ltd. | Addition product of lactone-modified epoxy resin with polyphenol and amino compounds |
| US5225461A (en) * | 1988-09-29 | 1993-07-06 | Kansai Paint Co., Ltd. | Amino group-containing, lactone-modified epoxy resin with polyisocyanate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57164116A (en) * | 1981-04-03 | 1982-10-08 | Daicel Chem Ind Ltd | Modified epoxy resin |
| JPS5832628A (en) * | 1981-08-20 | 1983-02-25 | Daicel Chem Ind Ltd | Curable epoxy resin composition |
-
1984
- 1984-03-06 JP JP4143084A patent/JPS60186524A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57164116A (en) * | 1981-04-03 | 1982-10-08 | Daicel Chem Ind Ltd | Modified epoxy resin |
| JPS5832628A (en) * | 1981-08-20 | 1983-02-25 | Daicel Chem Ind Ltd | Curable epoxy resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62164738A (en) * | 1986-01-14 | 1987-07-21 | Kansai Paint Co Ltd | Paint composition for polyurethane resin molding |
| JPH0588751B2 (en) * | 1986-01-14 | 1993-12-24 | Kansai Paint Co Ltd | |
| US5126413A (en) * | 1988-09-29 | 1992-06-30 | Kansai Paint Co., Ltd. | Addition product of lactone-modified epoxy resin with polyphenol and amino compounds |
| US5225461A (en) * | 1988-09-29 | 1993-07-06 | Kansai Paint Co., Ltd. | Amino group-containing, lactone-modified epoxy resin with polyisocyanate |
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