JPS6042469A - Photo-curable type temporary protective coating composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is suitable for use in temporarily preventing steel stock from rusting and whose coating film can be easily removed by an alkali, consisting of an acrylic copolymer contg. (meth)acrylic acid, an unsaturated compd. and a photopolymerization initiator. CONSTITUTION:A compsn. consists of 5-50pts.wt. acrylic copolymer contg. acrylic or methacrylic acid and having an acid value of 30-300KOHmg/g, 95- 50pts.wt. unsaturated compd. contg. at least one polymerizable double bond and 1-10pts.wt. photopolymerization initiator. Examples of the acrylic copolymers are those mainly composed of acrylic or methacrylic acid and other copolymerizable monomer. Pref. the copolymer has a weight-average NW of 5,000-100,000. When the MW is less than 5,000, performance such as resistance to corrosion and moisture is reduced, while when it exceeds 100,000, the viscosity of the compsn. is too high for practical use.

Description

【発明の詳細な説明】 ［発明の技術分野Ｊ 本発明は光硬化型一時保護被覆用組成物に関し、更に詳
しくは、鋼材の一時的防錆処理に有用でアルカリによる
脱膜が容易な光硬化型一時保護被覆用組成物に関する。Detailed Description of the Invention [Technical Field of the Invention J] The present invention relates to a photocurable temporary protective coating composition, and more particularly to a photocurable temporary protective coating composition that is useful for temporary rust prevention treatment of steel materials and is easy to remove with alkali. The present invention relates to a composition for temporary mold protection coating.

［発明の技術的背景とその問題点１ 現在、圧延鋼板、鋼管、線材及び棒鋼等のいわゆる鋼材
は、製造メーカーからユーザーに至るまでの期間におけ
る防錆を目的として鉱油型、乾性型の防錆剤又は水溶性
樹脂の防錆剤等で被覆処理され、形成された塗膜はユー
ザーにおける塗装の前処理工程でケイ酪ナトリウム、水
酸化すトリウム等のアルカリ水溶液にて脱膜される。[Technical background of the invention and its problems 1 Currently, so-called steel materials such as rolled steel plates, steel pipes, wire rods, and steel bars are treated with mineral oil type and dry type rust prevention for the purpose of rust prevention during the period from the manufacturer to the user. The coating film is coated with a rust preventive agent such as a water-soluble resin or a water-soluble resin, and the formed coating film is removed with an alkaline aqueous solution such as sodium sodium chloride or thorium hydroxide in a pre-treatment process for painting by the user.

しかしながら、現在使用されている鉱油型、乾性型及び
水溶性樹脂の防錆剤は、硬化後の塗面が乾燥せずにべた
ついたり、乾燥時間に長時間を要したり、更には防食性
、防湿性等の塗膜性能が不十分である等の問題点があっ
た。このため、短時間で硬化し、塗面がべとつかず、溶
剤揮散の心配のない一時保護被覆材が強く要望されてい
た。However, the currently used mineral oil type, dry type, and water-soluble resin rust preventive agents do not dry well after curing and become sticky, take a long time to dry, and have poor corrosion resistance. There were problems such as insufficient coating performance such as moisture resistance. For this reason, there has been a strong demand for a temporary protective coating that cures in a short time, does not leave a sticky coating, and does not have to worry about solvent volatilization.

そこで、紫外線等のいわゆる活性エネルギー線の照射に
より反応を起こす重合性不飽和基を有するモノマー又は
オリゴマーを一種又は二種以上適宜に組合わせた一時保
護被覆材の開発が進められているが、一般に、従来の一
時保護被覆材は、常温で短時間のうちに硬化するため残
留応力や体積収縮の影響を受け、金属等の基材に対する
密着性が不良となる欠点があり、このため、種々の添加
剤を併用して使用されているのが現状である。しかし、
鋼材に防錆剤を適用する際に密着促進剤等の添加剤を併
用した場合は、塗膜の耐湿性や塗料の安定性が不良とな
るため、これらの添加剤の併用は大きな制限を受けるこ
とになる。Therefore, efforts are being made to develop temporary protective coating materials that suitably combine one or more types of monomers or oligomers that have polymerizable unsaturated groups that react when irradiated with so-called active energy rays such as ultraviolet rays. Conventional temporary protective coating materials harden in a short time at room temperature and are affected by residual stress and volumetric shrinkage, resulting in poor adhesion to base materials such as metals. Currently, they are used in combination with additives. but,
If additives such as adhesion promoters are used together with rust preventives on steel materials, the moisture resistance of the paint film and stability of the paint will be poor, so there are major restrictions on the use of these additives in combination. It turns out.

また、防錆剤の脱膜工程においては、水酸化ナトリウム
又はオルトケイ酸ナトリウムの　１〜１０重着％水溶液
により容易に塗膜が脱膜されることが必要であるが、従
来の紫外線硬化型被覆材ではこの脱膜性と耐食性、耐湿
性等の塗膜性能のバランスをとることが困難であった。In addition, in the film removal process for rust preventive agents, it is necessary that the paint film be easily removed using a 1 to 10 weight percent aqueous solution of sodium hydroxide or sodium orthosilicate. It has been difficult to strike a balance between film removability and coating film performance such as corrosion resistance and moisture resistance.

すなわち、耐食性、耐湿性等の塗膜性能が良好なものは
脱膜性が不良であり、一方、脱膜性が良好なものは耐食
性、＋１　湿性等の塗膜性能が不良であるという欠点が
あった＠ したがって、以」二の欠点のない光硬化型一時保護被覆
材用の組成物（以下、これを光硬化型一時保護被覆用組
成物という）の開発が望まれていた。In other words, those with good coating film performance such as corrosion resistance and moisture resistance have poor film removability, while those with good film removability have the disadvantage of poor coating film performance such as corrosion resistance and +1 moisture resistance. Therefore, it has been desired to develop a composition for a photocurable temporary protective coating (hereinafter referred to as a composition for a photocurable temporary protective coating) that does not have the following drawbacks.

［発明の目的１ 本発明は、密着促進剤を併用することなく、脱膜性と耐
食性、耐湿性等の塗膜性能のバランスがとれた光硬化型
一時保護被覆用組成物を提供することを目的とする。[Objective of the Invention 1] The present invention aims to provide a photocurable temporary protective coating composition that has a good balance of film performance such as removability, corrosion resistance, and moisture resistance without using an adhesion promoter in combination. purpose.

［発明の概要１ 本発明者らは、紫外線硬化型一時防錆被覆材用の組成物
の開発に鋭意検討した結果、紫外線硬化型被覆材に使用
する重合体として、特定の範囲の酸価な有するアクリル
酸又はメタクリル酸及びそのエステル化合物の共重合体
を特定量配合すればよいことを見出し、本発明を完成す
るに至った。[Summary of the Invention 1] As a result of intensive studies into the development of compositions for UV-curable temporary rust-preventing coatings, the present inventors have found that a polymer with an acid value within a specific range can be used in UV-curable coatings. The present inventors have discovered that it is sufficient to blend a specific amount of a copolymer of acrylic acid or methacrylic acid and its ester compound, and have completed the present invention.

すなわち、本発明の光硬化型一時保護被覆用組成物は、 （Ａ）アクリル酸又はメタクリル酸を含み、しかも３０
〜３００　ＫＯＨｍｇ／ｇの範囲の酸価を有するアクリ
ル系共重合体５〜５０重量部 （Ｂ）重゛合可能な二重結合を１個以上有する不飽和化
合物８５〜５０重量部 （Ｃ）光重合開始剤１〜１０重量部 からなることを特徴とする。That is, the photocurable temporary protective coating composition of the present invention contains (A) acrylic acid or methacrylic acid, and
5 to 50 parts by weight of an acrylic copolymer having an acid value in the range of ~300 KOHmg/g (B) 85 to 50 parts by weight of an unsaturated compound having one or more polymerizable double bonds (C) Light It is characterized by comprising 1 to 10 parts by weight of a polymerization initiator.

以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.

本発明におけるアクリル系共重合体（Ａ）は、脱１１り
性と塗膜性能とのバランスを保つ上で、３０〜３ｏｏ　
ＫＯＨｍｇ／ｇの範囲の酸価を有していることが８賛で
ある。共重合体の酸価が３０　ＫＯ）ｌａｇ／ｇ未満の
場合は硬化後の塗膜をアルカリで容易に脱膜しにくくな
り、　３００　ＫＯＨｍｇ／ｇを超えると、塗膜の防錆
性、すなわち耐食性、耐湿性等の性能が低下する。かか
る範囲の酸価を有する共重合体とじては、アクリル酸又
はメタクリル酸及びこれらに共重合可能な単量体を主成
分としたアクリル系共重合体が使用される。The acrylic copolymer (A) in the present invention is 30 to 3 oo
It is highly recommended that it has an acid value in the range of KOHmg/g. If the acid value of the copolymer is less than 30 KOHmg/g, it will be difficult to remove the cured coating film with alkali, and if it exceeds 300 KOHmg/g, the rust prevention, that is, corrosion resistance, of the coating film will deteriorate. , performance such as moisture resistance deteriorates. As a copolymer having an acid value within this range, an acrylic copolymer containing as a main component acrylic acid or methacrylic acid and a monomer copolymerizable with these is used.

アクリル酸又はメタクリル酸に共重合可能な単１上体と
しては、例えば、アクリル酸メチル、メタクリル酩メチ
ル、アクリル酸エチル、メタクリル酸エチル、アクリル
酸ｎ−ブチル、メタクリル酸ｎ−ブチル、アクリル酩イ
ソブチル、メタクリル酸イソブチル、アクリル酪２−エ
チルヘキシル、メタクリル酸２−エチルヘキシル、アク
リル酸ラウリル、メタクリル酩ラウリル、アクリル酸ス
テアリル、メタクリル酸ステアリル、アクリル酩２−ヒ
ドロキシエチル、メタクリル酸２−ヒドロキシエチル、
アクリル酩２−ヒドロキシプロピル、メタクリル酸２−
ヒｌ’ロキシブロピル、アクリルＭｌ−ヒドロギシプチ
ル、メタクリル酸１−ヒドロキシブチル、アクリル酪ベ
ンジル、メタクリル醜ベンジル等のアクリル酪エステル
又はメタクリル酸エステル；アクリロニトリル、メタク
リロニトリル、アクリルアミド、メタクリルアミド等の
単量体が挙げられ、これらから選ばれる一種又は二種以
上の単量体を任意に配合することにより種々の塗膜性能
が発揮される。Examples of monomers copolymerizable with acrylic acid or methacrylic acid include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and isobutyl acrylate. , isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Acrylic acid 2-hydroxypropyl, methacrylic acid 2-
Acrylic butyesters or methacrylic acid esters such as hil'roxypropyl, acrylic Ml-hydroxyptyl, 1-hydroxybutyl methacrylate, acrylic butybenzyl, methacrylic ugly benzyl; monomers such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. By arbitrarily blending one or more monomers selected from these, various coating film performances can be exhibited.

上記共重合体の重量平均分子量は５，０００〜１００．
０００であることが好ましく、５，０００未満の場合は
耐食性、耐湿性等の性能が低下し易く、１００．０００
を超えると組成物の粘度が高くなりすぎて実用性に乏し
くなる。なお、これらの共重合体は、一般に知られてい
る重合法により得られるが、酸型量体の配合比率が高い
ため、懸濁重合法及び乳化重合法によってこれらの共重
合体を製造することは困難である。このため、溶液重合
法又は塊状重合法によって製造することが好ましい。The weight average molecular weight of the above copolymer is 5,000 to 100.
000 is preferable; if it is less than 5,000, performance such as corrosion resistance and moisture resistance tends to deteriorate, and 100.000
If it exceeds 20%, the viscosity of the composition becomes too high and becomes impractical. These copolymers can be obtained by generally known polymerization methods, but because the blending ratio of acid type polymers is high, it is difficult to produce these copolymers by suspension polymerization and emulsion polymerization methods. It is difficult. For this reason, it is preferable to manufacture by a solution polymerization method or a bulk polymerization method.

かかるアクリル系共重合体は、被覆用組成物中に５〜５
０重量部配合され、５重量部未満の場合は塗膜がアルカ
リによって容易に脱膜されにくくなり、５０重量部を超
えると得られる塗膜の耐食性、耐湿性等の性能が低下し
、一時保護被覆の目的が果せなくなる。Such an acrylic copolymer may be present in the coating composition in an amount of 5 to 5
If the amount is less than 5 parts by weight, the coating film will not be easily removed by the alkali, and if it exceeds 50 parts by weight, the corrosion resistance, moisture resistance, etc. of the resulting coating film will deteriorate, resulting in temporary protection. The purpose of the covering will no longer be achieved.

本発明における重合可能な二重結合を１個以上有する不
飽和化合物（Ｂ）としては、例えば、（１）アクリル酪
テトラヒドロフルフリル、メタクリル酎テトラヒドロフ
ルフリル、アクリル酸２−エチルヘキシル、メタクリル
酸２−エチルヘキシル、アクリル酸イソデシル、メタク
リル酸イソデシル、フェニルグリシジルエーテルのアク
リル酸又はメタクリル酸付加物等の単官能性不飽和化合
物； （Ｉ＋　）エチレングリコールジ（メタ）アクリレート
、ジエチレングリコールジ（メタ）アクリレート、トリ
エチレングリコールジ（メタ）アクリレート、テトラエ
チレングリコールジ（メタ）アクリレート、ネオペンチ
ルグリコールジ（メタ）アクリレート、トリメチロール
プロバントタ）アクリレート等の多官能性不飽和化合物
；（ｍ）ポリエステル形成性成分又はポリエステルと，
アクリロイルオキシ基形成性成分又はアクリロイルオキ
シ基を含有する化合物との反応生成物であって，一分子
当りアクリロイルオキシ基を平均−個以上有するポリエ
ステルポリアクリレーエボキシ樹脂とアクリル酸との反
応生成物であって、一分子当りアクリロイルオキシ基を
平均−個以上有するエポキシポリアクリレート、主鎖に
ウレタン結合を有し、一分子当りアクリロイルオキシ基
を平均−個以上有するウレタンポリアクリレート等のオ
リゴマー； 等が挙げられる。Examples of the unsaturated compound (B) having one or more polymerizable double bonds in the present invention include (1) acrylic butyratetrahydrofurfuryl, methacrylic butyrate tetrahydrofurfuryl, 2-ethylhexyl acrylate, methacrylic acid 2- Monofunctional unsaturated compounds such as ethylhexyl, isodecyl acrylate, isodecyl methacrylate, acrylic acid or methacrylic acid adducts of phenyl glycidyl ether; (I+) ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene Polyfunctional unsaturated compounds such as glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolprobanto)acrylate; (m) polyester-forming component or polyester and,
A reaction product between an acryloyloxy group-forming component or a compound containing an acryloyloxy group, and a reaction product between a polyester polyacrylate epoxy resin having an average of - or more acryloyloxy groups per molecule and acrylic acid. Examples include oligomers such as epoxy polyacrylates having an average of - or more acryloyloxy groups per molecule, and urethane polyacrylates having a urethane bond in the main chain and having an average of - or more acryloyloxy groups per molecule; It will be done.

かかる不飽和化合物としては、脱膜性と塗膜性能とのバ
ランスを保つ上で種々の組合わせが占えられるが、この
バランスが良好な系としてフェニルグリシジルエーテル
のアクリル酸付加物が好ましい。これらの不飽和化合物
は，被覆用組成物中に８５〜５０重量部配合され、９５
重量部を超えると塗膜がアルカリによって容易に脱膜さ
れにくくなり，５０改量部未満の場合は得られる塗膜の
耐食性、耐湿性等の性能が低下する。Various combinations of such unsaturated compounds can be used in order to maintain a balance between film removability and coating film performance, but an acrylic acid adduct of phenyl glycidyl ether is preferred as a system that provides a good balance. These unsaturated compounds are blended in the coating composition in an amount of 85 to 50 parts by weight, and 95 to 50 parts by weight.
If the amount exceeds 1 part by weight, the coating film will be difficult to be removed by the alkali, and if the amount is less than 50 parts by weight, the resulting coating film will have poor performance such as corrosion resistance and moisture resistance.

本発明における光重合開始剤（Ｃ）としては、例えば、
ベンゾイン、ベンゾインメチルエーテル、ベンゾインイ
ソプロピルエーテル、ベンゾインイソブチルエーテル、
ベンジル（ジフェニルジケトン）、ベンゾフェノン、２
−メチルアントラキノン、ベンジルジメチルケタール等
が挙げられる。Examples of the photopolymerization initiator (C) in the present invention include:
Benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
Benzyl (diphenyl diketone), benzophenone, 2
-Methyl anthraquinone, benzyl dimethyl ketal and the like.

これらは、一種又は二種以上が混合して用いられ、アク
リル系共重合体と不飽和化合物との合計；ｆｉｌｏＯ重
量部に対し　１〜１０重量部配合される。These are used singly or in combination of two or more, and are blended in an amount of 1 to 10 parts by weight based on the total weight of the acrylic copolymer and the unsaturated compound; filoO.

本発明の被覆用組成物には、通常配合し得るその他の樹
脂、例えば、エポキシ樹脂、ブチラール樹脂等を任意に
配合して諸性能に応じた被覆用組成物に変性することも
可能である．更に必要であれば常用されるリン酸系やア
ミン系の防錆剤を併用して一層防錆性を向上させること
も可能である。The coating composition of the present invention may optionally be blended with other resins that can be normally blended, such as epoxy resins, butyral resins, etc., to modify the coating composition according to various properties. Furthermore, if necessary, commonly used phosphoric acid-based or amine-based rust inhibitors may be used in combination to further improve the rust prevention properties.

本発明の被覆用組成物は、鋼材の表面に塗布され，紫外
線等、のいわゆる活性エネルギー線の照射により硬化せ
しめられた後、ユーザーに提供され、ユーザーにおける
塗装の前処理工程でアルカリ処理により説ＩＩＱされる
。The coating composition of the present invention is applied to the surface of a steel material, cured by irradiation with so-called active energy rays such as ultraviolet rays, and then provided to the user and treated with an alkali in the pre-painting process. IIQ will be given.

［発明の効果］ 本発明の被覆用組成物は、密着促進剤が配合されていな
いにもかかわらず、鋼材に対し優れた密着性を有し、し
かも耐食性、耐温性等の塗膜性能及びアルカリ処理によ
る脱膜性が優れている。したがって、該被覆用組成物は
、鋼材の一時的な防錆用保護被覆材として有用であり、
その工業的価値は極めて大である。[Effects of the Invention] The coating composition of the present invention has excellent adhesion to steel materials despite not containing an adhesion promoter, and has excellent coating film performance such as corrosion resistance and temperature resistance. Excellent film removability by alkali treatment. Therefore, the coating composition is useful as a temporary rust-preventive protective coating for steel materials,
Its industrial value is extremely large.

［発明の実施例Ｊ 以下の実施例中、部及び％とあるのは、それぞれ、重量
部及び重量％を表す。[Example J of the Invention In the following examples, parts and % represent parts by weight and % by weight, respectively.

実施例１ メタクリル酸メチル３０部、メタクリル酸ブチル５０部
及びアクリル酸２０部からなる混合溶液に重合開始剤と
してアゾビスイソブチロニトリル０．４部、連鎖移動剤
としてｔｅｒｔ−Ｆデシルメルカプタン０３部を溶解し
、これをセルキャスト中に仕込み、８０°Ｃの恒温水槽
で３時間重合せしめ、三成分からなる酸価１５Ｂ　ＫＯ
Ｈｍｇ／ｇ　、重量平均分子量２０．０００の共重合体
［ＩＩを得た。この共重合体［Ｉ］２０部をアクリル酸
テトラヒドロフルフリル７０部に溶解し、この溶液にダ
イヤビームＵＫＪ！２３（エポキシポリアクリレート、
三菱レイヨン株式会社製）１０部及びペンツインブチル
エーテル４部を混合して被覆用組成物を得た。Example 1 A mixed solution consisting of 30 parts of methyl methacrylate, 50 parts of butyl methacrylate, and 20 parts of acrylic acid was mixed with 0.4 parts of azobisisobutyronitrile as a polymerization initiator and 03 parts of tert-F decyl mercaptan as a chain transfer agent. This was dissolved in Celcast and polymerized for 3 hours in a constant temperature water bath at 80°C, resulting in a three-component acid value of 15B KO.
Copolymer [II] having a weight average molecular weight of 20.000 was obtained. 20 parts of this copolymer [I] was dissolved in 70 parts of tetrahydrofurfuryl acrylate, and Diabeam UKJ! 23 (epoxy polyacrylate,
(manufactured by Mitsubishi Rayon Co., Ltd.) and 4 parts of pent-in-butyl ether were mixed to obtain a coating composition.

この被覆用組成物を脱脂した軟鋼板上にパーコータにて
１１り厚１５〜２０ｐｍに塗装し、高圧水銀灯（三菱レ
イヨンエンジニアリング株式会社製、ＵＫ−２５０１）
８０Ｗ／ｃｍランプ１木で約２秒間照射した。This coating composition was applied to a degreased mild steel plate using a percoater to a thickness of 15 to 20 pm, and a high pressure mercury lamp (manufactured by Mitsubishi Rayon Engineering Co., Ltd., UK-2501) was used.
One tree was irradiated with an 80 W/cm lamp for about 2 seconds.

得られた被覆鋼板について、密着性、鉛筆硬１臭、杓撃
性、耐食性、削湿性、脱膜性に関する試験を行った。そ
の結果を表に示した。The obtained coated steel plate was tested for adhesion, pencil hard odor, punching resistance, corrosion resistance, moisture removal property, and film removability. The results are shown in the table.

実施例２ 実施例１でｆｌｌられた共重合体［１１２０部をフェニ
ルグリシジルエーテルのアクリル酸付加物７０部に溶解
したこと以外は、実施例１と同様にして被覆鋼板をｌ）
た。この被覆鋼板について実施例１と同様の試験に供し
、その結果を表に合わせて記載した。Example 2 A coated steel plate was prepared in the same manner as in Example 1, except that 1120 parts of the copolymer prepared in Example 1 was dissolved in 70 parts of acrylic acid adduct of phenyl glycidyl ether.
Ta. This coated steel plate was subjected to the same tests as in Example 1, and the results are listed in the table.

実施例３ 実施例２でｆｌ）られた共重合体［ＩＩのフェニルグリ
シジルエーテルのアクリル酸付加物溶液９０部に、タイ
ヤビームＵＫ−８１２３（エポキシポリアクリレート、
三菱レイヨン株式会社製）５部、エポキシ樹脂（油化シ
ェル化学社製、エピコート＃８２８）５部及びベンゾイ
ンブチルエーテル４部を混合して被覆用組成物を得た。Example 3 Tirebeam UK-8123 (epoxy polyacrylate,
A coating composition was obtained by mixing 5 parts of epoxy resin (Epicoat #828, manufactured by Yuka Shell Chemical Co., Ltd.), and 4 parts of benzoin butyl ether.

この被覆用組成物を用い実施例１と同様にして被覆鋼板
を得、該鋼板について実施例１と同様の試験を行い、そ
の結果を表に合わせて記載した。A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are listed in the table.

実施例４ 実施例１で得られた共重合体［ＩＩ５０部を、フェニル
グリシジルエーテルのアクリル酸イ＋Ｊ加物３０部及び
無水フタル酸とアクリル酸ヒドロキシエチルとの付加物
１０部に溶解し、この溶液に１．６−ヘキサンジオール
ジアクリレート　５部及びベンゾインブチルエーテル５
部を溶解混合し、被覆用組成物を得た。この被覆用組成
物を用いて実施例１と同様にして被覆鋼板を得、該鋼板
について実施例１と同様の試験を行い、その結果を表に
合わせて記載した。Example 4 50 parts of the copolymer [II obtained in Example 1] was dissolved in 30 parts of acrylic acid I+J adduct of phenyl glycidyl ether and 10 parts of an adduct of phthalic anhydride and hydroxyethyl acrylate. Add 5 parts of 1,6-hexanediol diacrylate and 5 parts of benzoin butyl ether to the solution.
The components were dissolved and mixed to obtain a coating composition. A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are shown in the table.

実施例５ 実施例１で得られた共重合体［１１５部を、アクリル酸
テトラヒドロフルフリル４５部及びフェニルグリシジル
エーテルのアクリル酸付加物３０部に溶解し、この溶液
にトリメチロールプロパントリアクリレート　５部、ダ
イヤビームＵＫ−６１０５（エポキシポリアクリレート
、三菱レイヨン株式会社製）５部、無水フタル酩とアク
リル酸ヒドロキシエチルとの付加物１０部及びベンゾイ
ンイソブチルエーテル５部を混合し、被覆用組成物を得
た。この被覆用組成物を用いて実施例１と同様にして被
覆鋼板を得、該鋼板について実施例１と同様の試験を行
い、その結果を表に合わせて記載した。Example 5 115 parts of the copolymer obtained in Example 1 was dissolved in 45 parts of tetrahydrofurfuryl acrylate and 30 parts of an acrylic acid adduct of phenylglycidyl ether, and 5 parts of trimethylolpropane triacrylate was added to this solution. , 5 parts of Diabeam UK-6105 (epoxy polyacrylate, manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts of an adduct of phthalic anhydride and hydroxyethyl acrylate, and 5 parts of benzoin isobutyl ether were mixed to obtain a coating composition. Ta. A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are shown in the table.

実施例６ メタクリル酸ブチル７５部、メタクリル酪２−ヒドロキ
シエチル５部及びメタクリル酸２０部からなる混合溶液
に１重合開始剤としてベンゾイルペルオキシド０．３部
を溶解し、実施例１と同様にして重合せしめ、酸価１３
０　ＫＯＨｍｇ／ｇ　、重量平均分子量５０．０００の
共重合体［ＩＩ　］を得た。この共重合体［ＩＩ］２０
部をフェニルグリシジルエーテルのアクリル酸付加物６
０部に溶解した。この溶液にエポキシ樹脂（油化シェル
化学社製、エピコート＃８２８）５部、タイヤビームＵ
Ｋ−８１２３（エポキシポリアクリレート、三菱レイヨ
ン株式会社製）５部、無水フタル酸とアクリル酸ヒドロ
キシエチルとの付加物１０部及びベンゾインインブチル
エーテル５部を混合し、被覆用組成物を得た。Example 6 0.3 parts of benzoyl peroxide as a polymerization initiator was dissolved in a mixed solution consisting of 75 parts of butyl methacrylate, 5 parts of methacrylic buty-2-hydroxyethyl, and 20 parts of methacrylic acid, and polymerization was carried out in the same manner as in Example 1. Seshime, acid value 13
A copolymer [II] having 0 KOHmg/g and a weight average molecular weight of 50.000 was obtained. This copolymer [II] 20
6 parts of acrylic acid adduct of phenyl glycidyl ether
Dissolved in 0 parts. To this solution, 5 parts of epoxy resin (manufactured by Yuka Shell Chemical Co., Ltd., Epicoat #828), Tire Beam U
5 parts of K-8123 (epoxy polyacrylate, manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts of an adduct of phthalic anhydride and hydroxyethyl acrylate, and 5 parts of benzoin butyl ether were mixed to obtain a coating composition.

この被覆用組成物を用いて実施例１と同様にして被覆鋼
板を得、該鋼板について実施例１と同様の試験を行い、
その結果を表に合わせて記載した。Using this coating composition, a coated steel plate was obtained in the same manner as in Example 1, and the steel plate was subjected to the same tests as in Example 1.
The results are listed in the table.

実施例７ 実施例６中の共重合体［ＩＩ　］の代わりに、メタクリ
ル酸メチル５０部、メタクリル酸ブチル４３部、アクリ
ル酸２−ヒドロキシエチル２部及びメタクリル酸５部を
用いて塊状重合法で共重合せしめた酸価３３ＫＯＨｍｇ
／ｇ　、　１ｍ平均分子量２０．０００１７）共重合体
［ｍ］を使用した。この共重合体［ＩＩ［］を用いたこ
と以外は、実施例６と同様にして被覆用組成物を得た。Example 7 In place of copolymer [II] in Example 6, 50 parts of methyl methacrylate, 43 parts of butyl methacrylate, 2 parts of 2-hydroxyethyl acrylate, and 5 parts of methacrylic acid were used to carry out bulk polymerization. Copolymerized acid value 33KOHmg
/g, 1m average molecular weight 20.00017) copolymer [m] was used. A coating composition was obtained in the same manner as in Example 6 except that this copolymer [II[] was used.

この被覆用組成物を用い実施例１と同様にして被覆鋼板
を得、該鋼板について実施例１と同様の試験を行い、そ
の結果を表に合わせて記載した。A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are listed in the table.

実施例８ 実施例６中の共重合体［ＩＩ　］の代わりに、メタクリ
ル酸メチル４０部、メタクリル酸エチル２０部及びアク
リル酸３５部を用いて塊状重合法で共重合せしめた酸価
２７３　ＫＯＨｍｇ／ｇ　、重量平均分子量ｉｏ、ｏｏ
。Example 8 In place of copolymer [II] in Example 6, 40 parts of methyl methacrylate, 20 parts of ethyl methacrylate, and 35 parts of acrylic acid were used to copolymerize by bulk polymerization to produce an acid value of 273 KOHmg/ g, weight average molecular weight io, oo
.

の共重合体［■〕を使用した。この共重合体［ｌＶ　］
を用いたこと以外は、実施例６と同様にして被覆用組成
物を得た。この被覆用組成物を用い実施例１と同様にし
て被覆鋼板を得、該鋼板について実施例１と同様の試験
を行い、その結果を表に合わせて記載した。A copolymer [■] was used. This copolymer [lV]
A coating composition was obtained in the same manner as in Example 6, except that the following was used. A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are listed in the table.

比較例１ メタクリル酸メチル８０部及びメタクリル酸ブチル２０
部からなる重量平均分子［４，０００の共重合体を懸濁
重合法により製造した。この共重合体を用い実施例６と
同様に、して被覆用組成物を得た。この被覆用組成物を
用い実施例１と同様にして被覆鋼板を得、該鋼板につい
て実施例１と同様の試験を行い、その結果を表に合わせ
て記載した。Comparative Example 1 80 parts of methyl methacrylate and 20 parts of butyl methacrylate
A copolymer with a weight average molecular weight of 4,000 parts was prepared by a suspension polymerization method. Using this copolymer, a coating composition was obtained in the same manner as in Example 6. A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are listed in the table.

比較例２ メタクリル酸メチル３０部、メタクリル酸ブチル２０部
及びメタクリル酸５０部からなる共重合体を塊状重合法
により製造し、酸価３２８　ＫＯＨｍｇ／ｇ　、重量平
均分子量１５０．ＯＯＱの共重合体を得た。この共重合
体を用い実施例６と同様にして被覆用組成物を得た。こ
の被覆用組成物を用い実施例１と同様にして被覆鋼板を
得、該鋼板について実施例１と同様の試験を行い、その
結果を表に合わせて記載した。Comparative Example 2 A copolymer consisting of 30 parts of methyl methacrylate, 20 parts of butyl methacrylate, and 50 parts of methacrylic acid was produced by a bulk polymerization method, and had an acid value of 328 KOHmg/g and a weight average molecular weight of 150. A copolymer of OOQ was obtained. A coating composition was obtained using this copolymer in the same manner as in Example 6. A coated steel plate was obtained using this coating composition in the same manner as in Example 1, and the same tests as in Example 1 were conducted on the steel plate, and the results are listed in the table.

比較例３ 実施例６中の共重合体［ＩＩ　］の代わりに、スチレン
−無水マレイン酸共重合体（ＡＲＣＯ社製５ＭＡ１００
０）を用い、実施例６と同様にして被覆用組成物を得た
。この被覆用組成物を用い実施例１と同様にして被覆鋼
板を得、該鋼板について実施例１と同様の試験を行い、
その結果を表に合わせて記載した。Comparative Example 3 Styrene-maleic anhydride copolymer (5MA100 manufactured by ARCO) was used instead of copolymer [II] in Example 6.
A coating composition was obtained in the same manner as in Example 6 using 0). Using this coating composition, a coated steel plate was obtained in the same manner as in Example 1, and the steel plate was subjected to the same tests as in Example 1.
The results are listed in the table.

試験条件 密着性試験　１ｍｍ　１４］のクロスカットで１００目
をとり、セロテープで剥離し、残り ・目で表示 鉛筆硬度試験　ＪＩＳ−５４００ 耐食性試験　ツルトスプレーテスト４８時間後の錆の発
生面積を％で表示 耐湿性試験　５％ＮａＯＨ水溶液に５０℃で３０分間浸
漬後の塗膜の剥離除去した面積 によりＯ１Δ及びＸで評価 ！ＩＩ’ＩＩ試験　デュポン式：坏インチＸ０．５ｋｇ
　Ｘ０ｃｍ Ｑ：異常なし ０〜Δ：衝撃部に若干われを 生じる ×；衝撃部にわれを生じるTest conditions Adhesion test Take 100 stitches with a cross cut of 1 mm 14], peel it off with cellophane tape, and display the remainder/mark Pencil hardness test JIS-5400 Corrosion resistance test Tsuruto spray test Display the area of rust after 48 hours in % Moisture resistance test Evaluated by O1Δ and II'II test DuPont type: 1 inch x 0.5 kg
X0cm Q: No abnormality 0 to Δ: Slight cracking occurs in the impact area ×; Cracking occurs in the impact area

Claims (3)

【特許請求の範囲】[Claims] （１）　（Ａ）アクリル酸又はメタクリル酸を含み、し
かも３０〜３００　ＫＯＨｍｇ／ｇの範囲の酸価を有す
るアクリル系共重合体５〜５０重量部 （Ｂ）重合可能な二重結合を１個以上有する不飽和化合
物９５〜５０重量部 （Ｃ）光重合開始剤１〜１０重量部 からなることを特徴とする光硬化型一時保護被覆用組成
物。(1) (A) 5 to 50 parts by weight of an acrylic copolymer containing acrylic acid or methacrylic acid and having an acid value in the range of 30 to 300 KOHmg/g (B) One polymerizable double bond A photocurable temporary protective coating composition comprising 95 to 50 parts by weight of an unsaturated compound having the above (C) and 1 to 10 parts by weight of a photopolymerization initiator. （２）アクリル系共重合体（Ａ）が。 （ａ）アクリル酸又はメタクリル酸と （ｂ）アクリル酸エステル又はメタクリル酸エステル の共重合体であって、重量平均分子量が５，０００〜１
００．θ００である特許請求の範囲第１項記載の光硬化
型一時保護被覆用組成物。(2) Acrylic copolymer (A). A copolymer of (a) acrylic acid or methacrylic acid and (b) acrylic ester or methacrylic ester, and has a weight average molecular weight of 5,000 to 1.
00. The photocurable temporary protective coating composition according to claim 1, wherein the composition has a temperature of θ00. （３）不飽和化合物（Ｂ）がフェニルグリシジルエーテ
ルのアクリル酎付加物である特許請求の範囲第１項記載
の光硬化型一時保護被覆用組成物。(3) The photocurable temporary protective coating composition according to claim 1, wherein the unsaturated compound (B) is an acrylic liquor adduct of phenyl glycidyl ether.