JP3355777B2 - Lubricity imparting agent and paint for outer surface of can containing the same - Google Patents
Lubricity imparting agent and paint for outer surface of can containing the sameInfo
- Publication number
- JP3355777B2 JP3355777B2 JP07692394A JP7692394A JP3355777B2 JP 3355777 B2 JP3355777 B2 JP 3355777B2 JP 07692394 A JP07692394 A JP 07692394A JP 7692394 A JP7692394 A JP 7692394A JP 3355777 B2 JP3355777 B2 JP 3355777B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- lubricity
- imparting agent
- silicone compound
- 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.)
- Expired - Lifetime
Links
Landscapes
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、新規にして有用なる潤
滑性付与剤に関する。本発明の潤滑性付与剤は、塗料を
はじめ、インキ、コーティング剤等の主剤および添加剤
として、広範に利用し得るものである。The present invention relates to a novel and useful lubricating agent . The lubricity imparting agent of the present invention can be widely used as a base agent and an additive for paints, inks, coating agents, and the like.
【0002】[0002]
【従来の技術】従来、潤滑性を有する塗膜を得るため
に、塗料組成中、潤滑性付与成分としてシリコーン化合
物が用いられてきた。しかし、これらのシリコーン化合
物は塗膜形成後に塗膜から脱離し、経時で塗膜の潤滑性
が低下するという欠点を有していた。塗膜の潤滑性の低
下は、特に、沸水等による浸漬処理後に顕著に現れる。
このようなシリコーン化合物の塗膜面からの脱離を防ぐ
ために、反応性の官能基を有するシリコーン化合物を用
いることが試みられている。反応性のシリコーン化合物
を、塗膜形成時に塗料組成中の反応性官能基を有する樹
脂成分と反応させ、塗膜面に固定させようというもので
ある。しかし、一般に、乾燥、熱硬化等による塗膜形成
過程は非常に短時間で行なわれるものであり、反応性の
シリコーン化合物と樹脂成分とが十分に反応することは
困難であった。2. Description of the Related Art Conventionally, in order to obtain a lubricating coating film, a silicone compound has been used as a lubricating component in a coating composition. However, these silicone compounds have the disadvantage that they are detached from the coating film after the formation of the coating film, and the lubricity of the coating film decreases over time. The decrease in lubricity of the coating film is particularly noticeable after immersion treatment with boiling water or the like.
Attempts have been made to use a silicone compound having a reactive functional group in order to prevent such a silicone compound from detaching from the coating surface. In this method, a reactive silicone compound is reacted with a resin component having a reactive functional group in a coating composition at the time of forming a coating film, and is fixed to a coating film surface. However, in general, a coating film forming process such as drying and heat curing is performed in a very short time, and it has been difficult for the reactive silicone compound and the resin component to sufficiently react with each other.
【0003】また、近年の環境保護の観点から塗料の水
性化が行なわれているが、従来用いられてきたシリコー
ン化合物では水性塗料に対する溶解性が悪く、エチレン
オキサイド鎖の導入等によるシリコーン化合物の水性化
が試みられている。しかしながら、このように水性化さ
れたシリコーン化合物は、耐水性が悪く、沸水等による
浸漬処理後の潤滑性は著しく低下した。[0003] In recent years, paints have been made water-soluble from the viewpoint of environmental protection. However, conventionally used silicone compounds have poor solubility in water-based paints. Has been attempted. However, the water-soluble silicone compound has poor water resistance, and the lubricity after the immersion treatment with boiling water or the like is significantly reduced.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、それ
を含有する塗膜が優れた潤滑性を有し、さらに塗膜の潤
滑性の低下が抑制された潤滑性付与剤の提供にある。SUMMARY OF THE INVENTION An object of the present invention is to provide a lubricity imparting agent in which a coating film containing the same has excellent lubricity and furthermore, a decrease in lubricity of the coating film is suppressed. .
【0005】[0005]
【課題を解決するための手段】すなわち、本発明は、反
応性官能基を有するシリコーン化合物の存在下で、トリ
アジン環を有するアミノ化合物をメチロール化し、さら
に必要に応じてエーテル化してなることを特徴とする潤
滑性付与剤を提供する。Means for Solving the Problems That is, the present invention provides anti
Provided is a lubricity imparting agent characterized in that an amino compound having a triazine ring is methylolated and, if necessary, etherified in the presence of a silicone compound having a reactive functional group .
【0006】本発明の潤滑性樹脂付与剤は、反応性官能
基を有するシリコーン化合物の存在下でトリアジン環を
有するアミノ化合物をメチロール化して得られるため、
メチロール化変性が施されたアミノ化合物とシリコーン
化合物との部分エーテル化や、生成したアミノ樹脂とシ
リコーン化合物との物理的からみあいが等が生じてい
る。したがって、単独では塗料樹脂に相溶性を有さない
シリコーン化合物を塗料成分として用いることができ、
シリコーン化合物の塗膜からの脱離による塗膜の潤滑性
の低下も抑制される。The lubricating resin imparting agent of the present invention comprises a reactive functional
It is obtained by methylolating an amino compound having a triazine ring in the presence of a silicone compound having a group ,
Partial etherification of the methylol-modified amino compound and the silicone compound, physical entanglement between the generated amino resin and the silicone compound, and the like occur. Therefore, a silicone compound having no compatibility with the paint resin alone can be used as the paint component,
A decrease in the lubricity of the coating film due to detachment of the silicone compound from the coating film is also suppressed.
【0007】シリコーン化合物としては、末端あるいは
側鎖に、水酸基、カルボキシル基およびグリシジル基か
ら選ばれる少なくとも一個の反応性官能基を有すること
が好ましい。これらのシリコーン化合物は、トリアジン
環を有するアミノ化合物やメチロール基と縮合するた
め、保存安定性および塗料樹脂との相溶性を向上させる
ことができる。[0007] The silicone compound preferably has at least one reactive functional group selected from a hydroxyl group, a carboxyl group and a glycidyl group at the terminal or side chain. Since these silicone compounds condense with an amino compound having a triazine ring or a methylol group, storage stability and compatibility with the coating resin can be improved.
【0008】また、下記一般式[I]で示される基を有
するシリコーン化合物を用いることも好ましい。一般式
[I]で示される基による疎水性、アンカー効果等のた
めに、潤滑性付与剤の耐水性を向上させ、沸水処理後等
のシリコーン化合物の脱離による潤滑性の低下を防ぐこ
とができる。It is also preferable to use a silicone compound having a group represented by the following general formula [I]. Due to the hydrophobicity, anchor effect, and the like of the group represented by the general formula [I], it is possible to improve the water resistance of the lubricity imparting agent and prevent a decrease in lubricity due to desorption of the silicone compound after boiling water treatment or the like. it can.
【0009】[0009]
【化2】 (式中、n1、n3は0または1、n2は 0〜150 の整数であ
り、n1、n2およびn3が全て0であることはない。R1は炭
素数30以下のアルキレン基、R2は炭素数34以下のアルキ
レン基、R3は炭素数18以下のアルキレン基、Xは水素あ
るいは水酸基を表す。) 具体的には、アルキル基、アルコキシル基、脂肪酸エス
テル基、またはラクトン類の開環重合によって得られる
ポリエステル基等を有するシリコーンオイル、脂肪酸変
性シリコーンオイル、オキシ酸変性シリコーンオイル等
が挙げられる。Embedded image (Wherein n1 and n3 are 0 or 1, n2 is an integer of 0 to 150, and n1, n2 and n3 are not all 0. R1 is an alkylene group having 30 or less carbon atoms, and R2 is a carbon number. An alkylene group of 34 or less, R3 is an alkylene group of 18 or less carbon atoms, X represents hydrogen or a hydroxyl group.) Specifically, it is obtained by ring-opening polymerization of an alkyl group, an alkoxyl group, a fatty acid ester group, or a lactone. Silicone oil having a polyester group or the like, fatty acid-modified silicone oil, oxyacid-modified silicone oil, and the like can be given.
【0010】トリアジン環を有するアミノ化合物として
は、特に限定されるものではなく、メラミン、ベンゾグ
アナミン、アセトグアナミン、スピログアナミン等が挙
げられる。本発明の潤滑性付与剤は、上記シリコーン化
合物の存在下で、上記トリアジン環を有するアミノ化合
物とアルデヒド類とを反応させてメチロール化し、さら
に必要に応じて生成したメチロール基とアルコール類の
水酸基とを脱水縮合させてエーテル化することにより得
ることができる。シリコーン化合物は、樹脂組成物中
0.1〜90重量%の範囲で用いることが好ましい。 0.1重
量%よりも少ないと良好な潤滑性を得ることが困難とな
り、90重量%よりも多いとアミノ化合物との相溶性が得
られにくくなる。The amino compound having a triazine ring is not particularly limited, and examples thereof include melamine, benzoguanamine, acetoguanamine, and spiro guanamine. Lubricity imparting agent of the present invention, in the presence of the silicone compound, by reacting the amino compound having a triazine ring and aldehydes to form methylol, and further formed, if necessary, a methylol group and a hydroxyl group of an alcohol. Can be obtained by dehydration-condensation and etherification. The silicone compound is contained in the resin composition
It is preferably used in the range of 0.1 to 90% by weight. If the amount is less than 0.1% by weight, it becomes difficult to obtain good lubricity. If the amount is more than 90% by weight, it becomes difficult to obtain compatibility with the amino compound.
【0011】トリアジン環を有するアミノ化合物のメチ
ロール化はホルムアルデヒドにより行なうことができ、
ホルムアルデヒド源としてはホルマリン、パラホルムア
ルデヒド等が挙げられる。アミノ化合物のメチロール化
は、酸性もしくはアルカリ性の反応雰囲気下、40〜150
℃において、上記アミノ化合物にアルデヒド類の適当量
を添加し反応せしめることにより行うことができる。こ
の場合、上記アミノ化合物は、単独あるいは2種類以上
の混合物として用いることができる。また、アルデヒド
類の添加量は、所望するアミノ化合物のメチロール化度
により適宜調整される。適正なメチロール化度は、用い
るアミノ化合物の種類により一概には言えないが、アミ
ノ化合物の有する活性水素1当量当たり 0.5当量以上の
アルデヒド類を反応させることが好ましいと考えられ
る。メチロール化度が低すぎると、得られるアミノ樹脂
に熱硬化性が発現しない場合があり好ましくない。Methylolation of an amino compound having a triazine ring can be carried out with formaldehyde.
Formaldehyde sources include formalin, paraformaldehyde and the like. The methylolation of the amino compound is carried out in an acidic or alkaline reaction atmosphere under the conditions of 40 to 150.
The reaction can be carried out by adding an appropriate amount of an aldehyde to the amino compound and reacting the mixture at a temperature of ° C. In this case, the amino compounds can be used alone or as a mixture of two or more. The amount of the aldehyde added is appropriately adjusted depending on the desired degree of methylolation of the amino compound. The appropriate degree of methylolation cannot be unconditionally determined depending on the type of amino compound used, but it is considered preferable to react aldehydes in an amount of 0.5 equivalent or more per equivalent of active hydrogen contained in the amino compound. If the degree of methylolation is too low, the resulting amino resin may not exhibit thermosetting properties, which is not preferable.
【0012】メチロール化されたトリアジン環を有する
アミノ化合物は、必要に応じて、アルコール類と脱水を
行ないながら縮合せしめ、エーテル化される。エーテル
化する際には、蟻酸、酢酸等の酸触媒を添加してもよ
い。アルコール類は、アミノ化合物に導入されたメチロ
ール基1当量に対して 0.5当量以上用いることが好まし
く、反応時の溶媒として用いることもできる。 0.5当量
よりも少ないと、メチロール化されたアミノ化合物同士
の縮合が著しく進み分子量が上がり、不溶化する場合も
あり好ましくない。The methylol-containing amino compound having a triazine ring is optionally condensed with alcohols while being dehydrated and etherified. At the time of etherification, an acid catalyst such as formic acid or acetic acid may be added. The alcohol is preferably used in an amount of 0.5 equivalent or more based on 1 equivalent of the methylol group introduced into the amino compound, and can be used as a solvent during the reaction. If the amount is less than 0.5 equivalent, the condensation between the methylolated amino compounds remarkably progresses, the molecular weight increases, and it may be insoluble, which is not preferable.
【0013】アルコール類としては、メタノール、エタ
ノール、プロパノール、ブタノール、エチレングリコー
ルノモメチルエーテル、エチレングリコールモノエエチ
ルエーテル、エチレングリコールモノプロピルエーテ
ル、エチレングリコールモノブチルエーテル、エチレン
グリコール、ジエチレングリコール、トリエチレングリ
コール、プロピレングリコール、ブタンジオール、エチ
レングリコールモノメチルエーテル、エチレングリコー
ルモノエチルエーテル、エチレングリコールモノイソプ
ロピルエーテル、エチレングリコールモノブチルエーテ
ル、エチレングリコールモノヘキシルエーテル等が挙げ
られる。Examples of the alcohols include methanol, ethanol, propanol, butanol, ethylene glycol nomomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol, diethylene glycol, triethylene glycol, and propylene. Glycol, butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and the like.
【0014】本発明の潤滑性付与剤は、塗料、インキ等
の主剤として用いられるが、添加剤として他の樹脂と配
合して用いることもできる。他の樹脂としては、一般に
塗料、インキ等に用いられる樹脂であれば特に限定され
るものではなく、アクリル系樹脂、アルキド樹脂、ポリ
エステル樹脂、ウレタン樹脂、ビニル樹脂、ポリアミド
樹脂、エポキシ樹脂、アミノ樹脂、フェノール樹脂等が
挙げられる。他の樹脂と潤滑性付与剤の配合比として
は、他の樹脂 100重量部に対して潤滑性付与剤中のシリ
コーン化合物が 0.1〜10重量部が好ましい。また、本発
明の潤滑性付与剤には、必要に応じて、着色等のための
染料や顔料、硬化物物性改良のための各種添加剤類、例
えばフィラー類、レベリング剤、硬化剤、難燃剤、増粘
剤等を含有させることができる。The lubricity- imparting agent of the present invention is used as a main component of paints, inks and the like, but can also be used as an additive in combination with other resins. Other resins are not particularly limited as long as they are generally used for paints, inks, etc., and include acrylic resins, alkyd resins, polyester resins, urethane resins, vinyl resins, polyamide resins, epoxy resins, and amino resins. And phenolic resins. The mixing ratio of the lubricating agent to the other resin is preferably 0.1 to 10 parts by weight of the silicone compound in the lubricating agent with respect to 100 parts by weight of the other resin. Further, the lubricity imparting agent of the present invention, if necessary, dyes and pigments for coloring and the like, various additives for improving the properties of the cured product, such as fillers, leveling agents, curing agents, flame retardants , A thickener and the like.
【0015】[0015]
セパラブル4口フラスコに、温度制御用レギュレータ
ー、冷却管、撹拌装置を取り付け、ベンゾグアナミン 5
61部、パラホルムアルデヒド 288部、水酸基変性シリコ
ーンオイル(チッソ社製「サイラプレーンFM4421」)212
部、n-ブタノール1060部を仕込み、トリエチルアミンに
よりpHを約9に調整し、液温を90℃に保ちながら約3
時間反応を行い、キシレン 100部を添加し、共沸脱水し
ながら約3時間反応を行ない、不揮発分約70%の付与剤
A−1を得た。Attach a regulator for temperature control, a condenser, and a stirrer to the separable four-necked flask.
61 parts, 288 parts of paraformaldehyde, hydroxyl-modified silicone oil ("Silaprene FM4421" manufactured by Chisso) 212
Parts, n-butanol (1060 parts), pH was adjusted to about 9 with triethylamine, and about 3
The reaction was carried out for an hour, 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration to obtain a grant agent A-1 having a nonvolatile content of about 70%.
【0016】〔製造例2〕 製造例1と同様の反応装置に、ベンゾグアナミン 561
部、ホルムアルデヒド含有イソプロピルアルコール40%
溶液(広栄化学社製「ホルミットIP」)900部、カルボキ
シル基変性シリコーンオイル(信越化学工業社製「X-22
-3701E」)48部、イソプロピルアルコール 430部を仕込
み、撹拌しながら徐々に昇温し還流温度で30分加熱し
た。蟻酸1部を仕込み、引き続き加熱し還流脱水しなが
ら8時間かけて反応した後、冷却し、ブチルセロソルブ
で調整し、不揮発分約70%の付与剤A−2を得た。Production Example 2 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Part, formaldehyde-containing isopropyl alcohol 40%
900 parts of solution (“Hormit IP” manufactured by Koei Chemical Co., Ltd.) and carboxyl group-modified silicone oil (“X-22 manufactured by Shin-Etsu Chemical Co., Ltd.”
-3701E "), and 430 parts of isopropyl alcohol were charged, and the temperature was gradually increased while stirring, and the mixture was heated at the reflux temperature for 30 minutes. After 1 part of formic acid was charged, the reaction was continued for 8 hours while heating and refluxing dehydration, followed by cooling and adjusting with butyl cellosolve to obtain grant agent A-2 having a nonvolatile content of about 70%.
【0017】〔製造例3〕 製造例1と同様の反応装置に、メラミン 265部、ベンゾ
グアナミン 168部、パラホルムアルデヒド 486部、グリ
シジル基変性シリコーンオイル(チッソ社製「サイラプ
レーンFM5521」)102部、ブチルセロソルブ1020部を仕込
み、10%水酸化ナトリウム水溶液でpHを約10に調整
し、液温を90℃に保ちながら約3時間反応を行なった。
その後、キシレン 100部を添加し、共沸脱水しながら約
3時間反応を行ない、不揮発分約70%の付与剤A−3を
得た。Production Example 3 In the same reactor as in Production Example 1, 265 parts of melamine, 168 parts of benzoguanamine, 486 parts of paraformaldehyde, 102 parts of a glycidyl group-modified silicone oil (“Silaprene FM5521” manufactured by Chisso), 102 parts of butyl cellosolve 1020 parts were charged, the pH was adjusted to about 10 with a 10% aqueous sodium hydroxide solution, and the reaction was carried out for about 3 hours while maintaining the liquid temperature at 90 ° C.
Thereafter, 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropically dehydrating to obtain a grant agent A-3 having a nonvolatile content of about 70%.
【0018】〔製造例4〕 製造例1と同様の反応装置に、スピログアナミン 651
部、ホルムアルデヒド含有メタノール40%溶液(広栄化
学社製「ホルミットMH」)900部、ステアリン酸変性シリ
コーンオイル(チッソ社製「PS053 」)112部を仕込み、
ナトリウムメチラートにてpHを約8に調整し、60℃で
60分間加熱した。硝酸2部を仕込み、引き続き加熱し60
℃で10時間反応した後、水酸化ナトリウムを中和量入
れ、水層を分離除去した後メタノールおよび水を減圧除
去し、更にブチルセロソルブで調整し、不揮発分約70%
の付与剤A−4を得た。[Production Example 4] In the same reactor as in Production Example 1, spirologamine 651 was added.
Parts, 900 parts of a formaldehyde-containing methanol 40% solution (“Hormit MH” manufactured by Koei Chemical Co., Ltd.) and 112 parts of stearic acid-modified silicone oil (“PS053” manufactured by Chisso) were charged.
Adjust the pH to about 8 with sodium methylate and at 60 ° C
Heated for 60 minutes. Charge 2 parts of nitric acid and continue heating to 60
After reacting at 10 ° C. for 10 hours, neutralized amount of sodium hydroxide was added, and the aqueous layer was separated and removed. Then, methanol and water were removed under reduced pressure, and further adjusted with butyl cellosolve.
Was obtained.
【0019】〔製造例5〕 製造例1と同様の反応装置に、ベンゾグアナミン 561
部、パラホルムアルデヒド 288部、アルキル変性シリコ
ーンオイル(信越化学工業社製「KF-412」)17部、n-ブ
タノール 870部を仕込み、ジメチルエタノールアミンに
よりpHを約9に調整し、液温を90℃に保ちながら約3
時間反応を行なった。その後、キシレン 100部を添加
し、共沸脱水しながら約3時間反応を行ない、不揮発分
約70%の付与剤A−5を得た。Production Example 5 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Parts, 288 parts of paraformaldehyde, 17 parts of alkyl-modified silicone oil (“KF-412” manufactured by Shin-Etsu Chemical Co., Ltd.) and 870 parts of n-butanol, the pH was adjusted to about 9 with dimethylethanolamine, and the liquid temperature was adjusted to 90. About 3
A time reaction was performed. Thereafter, 100 parts of xylene was added and the reaction was carried out for about 3 hours while azeotropically dehydrating to obtain a grant agent A-5 having a nonvolatile content of about 70%.
【0020】〔製造例6〕 製造例1と同様の反応装置に、メラミン 113部、ベンゾ
グアナミン 393部、パラホルムアルデヒド 331部、高級
アルコキシ基変性シリコーンオイル(信越化学工業社製
「X-22-801B 」)209部、n-ブタノール1050部を入れ、ト
リエチルアミンでpHを約9に調整し、液温を90℃に保
ちながら約3時間反応を行なった。その後、キシレン 1
00部を添加し、共沸脱水しながら約3時間反応を行な
い、不揮発分約70%の付与剤A−6を得た。[Production Example 6] In the same reactor as in Production Example 1, 113 parts of melamine, 393 parts of benzoguanamine, 331 parts of paraformaldehyde, and a higher alkoxy group-modified silicone oil (“X-22-801B” manufactured by Shin-Etsu Chemical Co., Ltd.) 209 parts) and 1050 parts of n-butanol were added, the pH was adjusted to about 9 with triethylamine, and the reaction was carried out for about 3 hours while maintaining the liquid temperature at 90 ° C. Then xylene 1
The reaction was carried out for about 3 hours while azeotropic dehydration was carried out to obtain imparting agent A-6 having a nonvolatile content of about 70%.
【0021】〔製造例7〕 製造例1と同様の反応装置に、ベンゾグアナミン 561
部、パラホルムアルデヒド 288部、高級脂肪族エステル
変性シリコーンオイル(信越化学工業社製「KF-910」)
94部、ブチルセロソルブ1010部を入れ、トリエチルアミ
ンによりpHを約9に調整し、液温を90℃に保ちながら
約3時間反応を行い、キシレン 100部を添加し、共沸脱
水しながら約3時間反応を行ない、不揮発分約70%の付
与剤A−7を得た。Production Example 7 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Part, 288 parts of paraformaldehyde, higher aliphatic ester modified silicone oil (“KF-910” manufactured by Shin-Etsu Chemical Co., Ltd.)
Add 94 parts and 1010 parts of butyl cellosolve, adjust the pH to about 9 with triethylamine, carry out the reaction for about 3 hours while maintaining the liquid temperature at 90 ° C., add 100 parts of xylene, and react for about 3 hours while azeotropically dehydrating. And apply about 70% non-volatile content .
Additive A-7 was obtained.
【0022】〔製造例8〕 製造例1と同様の反応装置に、メラミン 378部、パラホ
ルムアルデヒド 540部、アルキル基、水酸基変性シリコ
ーンオイル(末端水酸基変性ポリジメチル−メチルデシ
ルシロキサン、Si数60、メチルデシルシロキサンユニッ
ト48〜52モル%)102部、n-ブタノール1020部を入れ、10
%水酸化ナトリウム水溶液でpHを約10に調整し、液温
を90℃に保ちながら約3時間反応を行なった。その後、
キシレン100部を添加し、共沸脱水しながら約3時間反
応を行ない、不揮発分約70%の付与剤A−8を得た。[Production Example 8] In a reaction apparatus similar to that of Production Example 1, 378 parts of melamine, 540 parts of paraformaldehyde, an alkyl group and a hydroxyl-modified silicone oil (polydimethyl-methyldecylsiloxane modified with a hydroxyl group at a terminal, 60 Si, methyl (Decyl siloxane unit 48-52 mol%) 102 parts, n-butanol 1020 parts
The pH was adjusted to about 10 with a 10% aqueous sodium hydroxide solution, and the reaction was carried out for about 3 hours while maintaining the liquid temperature at 90 ° C. afterwards,
100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration to obtain a grant agent A-8 having a nonvolatile content of about 70%.
【0023】〔製造例9〕 製造例1と同様の反応装置に、ベンゾグアナミン 374
部、パラホルムアルデヒド 192部、末端カプロラクトン
変性シリコーンオイル(Si数60、ラクトン鎖数40のポリ
ジメチルシロキサン)377部、n-ブタノール 940部を入
れ、トリエチルアミンでpHを約9に調整し、液温を90
℃に保ちながら約3時間反応を行なった。その後、キシ
レン 100部を添加し、共沸脱水しながら約3時間反応を
行ない、不揮発分約70%の付与剤A−9を得た。[Production Example 9] In the same reactor as in Production Example 1, benzoguanamine 374 was added.
Parts, 192 parts of paraformaldehyde, 377 parts of caprolactone-modified silicone oil (polydimethylsiloxane with 60 Si and 40 lactone chains) and 940 parts of n-butanol, adjust the pH to about 9 with triethylamine, and adjust the liquid temperature. 90
The reaction was carried out for about 3 hours while maintaining the temperature. Thereafter, 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration to obtain a grant agent A-9 having a nonvolatile content of about 70%.
【0024】〔製造例10〕 製造例1と同様の反応装置に、ベンゾグアナミン 561
部、ホルムアルデヒド 288部、水酸基変性シリコーンオ
イル(信越化学工業社製「KF6003」)1272部を仕込み、
トリエチルアミンによりpHを約9に調整し、液温を90
℃に保ちながら約3時間反応を行い、キシレン 100部を
添加し、共沸脱水しながら約3時間反応を行ない、不揮
発分約70%の付与剤A−10を得た。Production Example 10 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Parts, 288 parts of formaldehyde and 1272 parts of hydroxyl-modified silicone oil ("KF6003" manufactured by Shin-Etsu Chemical Co., Ltd.)
The pH was adjusted to about 9 with triethylamine, and the liquid temperature was adjusted to 90.
The reaction was carried out for about 3 hours while the temperature was maintained at 0 ° C., and 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration was carried out to obtain grant agent A-10 having a nonvolatile content of about 70%.
【0025】〔製造例11〕製造例1と同様の反応装置
に、ブチルセロソルブ 240部を仕込み、約90℃に昇温し
反応容器内を窒素置換した後、滴下管よりスチレン 168
部、エチルアクリレート 112部、2-エチルヘキシルアク
リレート84部、2-ヒドロキシエチルメタクリレート 112
部、N-メトキシメチルアクリルアミド56部、アクリル酸
28部、有機過酸化物(日本油脂社製「パーブチルO」)
28部を3時間かけて滴下した。滴下終了1時間後に、有
機過酸化物「パーブチルO」 2.8部を添加し、更に1時
間反応を継続した。不揮発分約70%の樹脂溶液B−1が
得られた。[Production Example 11] 240 parts of butyl cellosolve was charged into the same reactor as in Production Example 1, the temperature was raised to about 90 ° C, and the inside of the reaction vessel was purged with nitrogen.
Parts, ethyl acrylate 112 parts, 2-ethylhexyl acrylate 84 parts, 2-hydroxyethyl methacrylate 112
Parts, N-methoxymethylacrylamide 56 parts, acrylic acid
28 parts, organic peroxide ("Perbutyl O" manufactured by NOF Corporation)
28 parts were added dropwise over 3 hours. One hour after the completion of the dropwise addition, 2.8 parts of an organic peroxide "perbutyl O" was added, and the reaction was continued for another hour. A resin solution B-1 having a nonvolatile content of about 70% was obtained.
【0026】〔実施例1〜10、比較例1〜3〕 製造例1〜10で得られた付与剤と製造例11で得られた樹
脂溶液を用いて表1に示す組成(固形分比)にしたがっ
て各成分を混合した後、実施例1、5、6、7、9、1
0、比較例1はブチルセロソルブで固形分35%に調整
し、実施例2、3、4、8、比較例2、3はブチルセロ
ソルブおよび水を添加して有機溶剤量を15%、固形分35
%に調整した。これらにパラトルエンスルホン酸を 0.3
%添加して水性塗料組成物を得た。この塗料をナチュラ
ルロールコーターにて、TFS板(クロム処理鋼板)上
に塗装し、 180℃で10分間焼付け硬化させた。膜厚6〜
8μmの塗工膜を得た。Examples 1 to 10 and Comparative Examples 1 to 3 Compositions (solid content ratio) shown in Table 1 using the imparting agents obtained in Production Examples 1 to 10 and the resin solution obtained in Production Example 11 After mixing the components according to Example 1, 5, 6, 7, 9, 1
0, Comparative Example 1 was adjusted to a solid content of 35% with butyl cellosolve, and Examples 2, 3, 4, 8, and Comparative Examples 2 and 3 were added with butyl cellosolve and water to reduce the organic solvent amount to 15% and a solid content of 35%.
%. Add 0.3% of paratoluenesulfonic acid to these
% To obtain an aqueous coating composition. This paint was applied on a TFS plate (chrome-treated steel plate) using a natural roll coater, and baked and cured at 180 ° C. for 10 minutes. Film thickness 6 ~
An 8 μm coating film was obtained.
【0027】[0027]
【表1】 [Table 1]
【0028】*1 エチルエーテル化ベンゾグアナミン
樹脂、三井サイアナミッド社製 *2 部分ブチルエーテル化ベンゾグアナミン樹脂、三
井サイアナミッド社製 *3 メチルエーテル化メラミン樹脂、三井サイアナミ
ッド社製 *4 ブチルエーテル化メラミン樹脂、三井サイアナミ
ッド社製 *5 サイラプレーンFM4421* 1 Ethyl etherified benzoguanamine resin, manufactured by Mitsui Cyanamid Inc. * 2 Partially butyl etherified benzoguanamine resin, manufactured by Mitsui Cyanamid Inc. * 3 Methyl etherified melamine resin, manufactured by Mitsui Cyanamid Inc. * 4 Butyl etherified melamine resin, manufactured by Mitsui Cyanamid Inc. * 5 Thyraplane FM4421
【0029】実施例および比較例で作成した塗料の安定
性および硬化塗膜の沸水処理前後の滑り性について調べ
た結果を表2に示す。各試験方法は下記の通りである。 塗料安定性;塗料を50℃で1週間保存後、塗料中の樹脂
のゲル化、分離の状態を観察した。 塗膜滑り性;表面性測定機(新東科学社製「HEIDON-14
」)を用いて、荷重200g、ボール圧子φ10mm、移動速
度 100mm/分の条件にて、25℃、50%RHで動摩擦係数を
測定した。30分沸水処理後の硬化塗膜においても同様の
試験を行なった。 ◎−動摩擦係数 0.1未満 ○−動摩擦係数 0.1以上 0.2未満 ×−動摩擦係数 0.2以上Table 2 shows the results of examining the stability of the paints prepared in Examples and Comparative Examples and the slipperiness of the cured coating film before and after the boiling water treatment. Each test method is as follows. Paint stability: After the paint was stored at 50 ° C. for one week, the state of gelation and separation of the resin in the paint was observed. Coating film sliding property; Surface property measuring device (“HEIDON-14” manufactured by Shinto Kagaku
The dynamic friction coefficient was measured at 25 ° C. and 50% RH under the conditions of a load of 200 g, a ball indenter φ of 10 mm, and a moving speed of 100 mm / min. The same test was performed on the cured coating film after the boiling water treatment for 30 minutes. ◎-Dynamic friction coefficient less than 0.1 ○-Dynamic friction coefficient 0.1 or more and less than 0.2 ×-Dynamic friction coefficient 0.2 or more
【0030】[0030]
【表2】 [Table 2]
【0031】[0031]
【発明の効果】本発明の潤滑性付与剤は、保存安定性お
よび塗料等に用いられる樹脂との相溶性に優れている。
また、本発明の潤滑性付与剤を含有する塗膜は、潤滑性
付与剤中のシリコーン化合物の脱離による塗膜の潤滑性
の低下が抑制されており、沸水処理等を行っても塗膜の
潤滑性の低下が認められない。したがって、本発明の潤
滑性付与剤は、塗料を始め、インキ、コーティング剤用
などのバインダーとして、広範な用途に利用することが
でき、工業上極めて有用である。The lubricity imparting agent of the present invention is excellent in storage stability and compatibility with resins used for paints and the like.
Further, the coating film containing the lubricity imparting agent of the present invention has lubricity.
A decrease in the lubricity of the coating film due to detachment of the silicone compound in the imparting agent is suppressed, and no decrease in the lubricity of the coating film is observed even when a boiling water treatment or the like is performed. Therefore, the lubricity imparting agent of the present invention can be used for a wide range of applications as a binder for paints, inks, coating agents, and the like, and is industrially extremely useful.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI C09D 7/12 C09D 7/12 C10M 169/04 C10M 169/04 //(C10M 169/04 107:50 107:50 133:42 133:42) C10N 30:06 C10N 30:06 50:08 50:08 (58)調査した分野(Int.Cl.7,DB名) C08L 83/00 - 83/16 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI C09D 7/12 C09D 7/12 C10M 169/04 C10M 169/04 // (C10M 169/04 107: 50 107: 50 133: 42 133: 42) C10N 30:06 C10N 30:06 50:08 50:08 (58) Field surveyed (Int. Cl. 7 , DB name) C08L 83/00-83/16
Claims (5)
基から選ばれる少なくとも一個の反応性官能基を有する
シリコーン化合物の存在下で、トリアジン環を有するア
ミノ化合物をメチロール化してなることを特徴とする潤
滑性付与剤。1. A hydroxyl group, a carboxyl group and glycidyl.
A lubricity imparting agent obtained by converting an amino compound having a triazine ring into methylol in the presence of a silicone compound having at least one reactive functional group selected from the group consisting of:
基から選ばれる少なくとも一個の反応性官能基を有する
シリコーン化合物の存在下で、トリアジン環を有するア
ミノ化合物をメチロール化したのちエーテル化してなる
ことを特徴とする潤滑性付与剤。2. A hydroxyl group, a carboxyl group and glycidyl.
A lubricating agent characterized in that an amino compound having a triazine ring is methylolated and then etherified in the presence of a silicone compound having at least one reactive functional group selected from the groups .
示される基を有することを特徴とする請求項1または2
記載の潤滑性付与剤。 【化1】 (式中、n1、n3は0または1、n2は 0〜150 の整数であ
り、n1、n2およびn3が全て0であることはない。R1は炭
素数30以下のアルキレン基、R2は炭素数34以下のアルキ
レン基、R3は炭素数18以下のアルキレン基、Xは水素あ
るいは水酸基を表す。)3. A silicone compound according to claim 1 or 2 characterized by having a group represented by the following general formula [I]
The lubricity imparting agent as described in the above. Embedded image (Wherein n1 and n3 are 0 or 1, n2 is an integer of 0 to 150, and n1, n2 and n3 are not all 0. R1 is an alkylene group having 30 or less carbon atoms, and R2 is a carbon number. An alkylene group of 34 or less, R3 represents an alkylene group having 18 or less carbon atoms, and X represents hydrogen or a hydroxyl group.)
グリシジル基から選ばれる少なくとも一個の反応性官能
基を有するシリコーン化合物を 0.1〜90重量%用いるこ
とを特徴とする請求項1ないし3いずれか記載の潤滑性
付与剤。During wherein imparting agent, a hydroxyl group, a carboxyl group and
At least one reactive function selected from glycidyl groups
Claims 1, characterized by using 0.1 to 90 wt% of a silicone compound having a group 3 lubricity according to any one
Granting agent .
与剤を含むことを特徴とする缶外面用塗料。5. A claims 1 to with Lubrication of 4 according any
A paint for the outer surface of a can, characterized by containing an additive .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP07692394A JP3355777B2 (en) | 1994-04-15 | 1994-04-15 | Lubricity imparting agent and paint for outer surface of can containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP07692394A JP3355777B2 (en) | 1994-04-15 | 1994-04-15 | Lubricity imparting agent and paint for outer surface of can containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07278436A JPH07278436A (en) | 1995-10-24 |
JP3355777B2 true JP3355777B2 (en) | 2002-12-09 |
Family
ID=13619239
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP07692394A Expired - Lifetime JP3355777B2 (en) | 1994-04-15 | 1994-04-15 | Lubricity imparting agent and paint for outer surface of can containing the same |
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Country | Link |
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JP (1) | JP3355777B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4622245B2 (en) * | 2004-01-07 | 2011-02-02 | Dic株式会社 | Resin composition for paint, paint and paint comprising the resin composition for paint |
JP7062233B2 (en) * | 2018-03-08 | 2022-05-06 | 株式会社ソミックマネージメントホールディングス | Grease composition for ball joints |
-
1994
- 1994-04-15 JP JP07692394A patent/JP3355777B2/en not_active Expired - Lifetime
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JPH07278436A (en) | 1995-10-24 |
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