JP3516833B2 - Super weather resistant paint composition - Google Patents
Super weather resistant paint compositionInfo
- Publication number
- JP3516833B2 JP3516833B2 JP12330597A JP12330597A JP3516833B2 JP 3516833 B2 JP3516833 B2 JP 3516833B2 JP 12330597 A JP12330597 A JP 12330597A JP 12330597 A JP12330597 A JP 12330597A JP 3516833 B2 JP3516833 B2 JP 3516833B2
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- Japan
- Prior art keywords
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- coating
- coating composition
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- parts
- Prior art date
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は耐候性に極めて優れ
た塗料組成物に関する。TECHNICAL FIELD The present invention relates to a coating composition having extremely excellent weather resistance.
【０００２】[0002]
【従来の技術】塗料分野においては、特に屋外構造物用
途等への適用に際し、その耐候性の向上が重要な課題と
なっている。これまでに耐候性に優れた塗料としてはフ
ッ素樹脂系塗料、アクリルシリコン系塗料等が知られて
いる。しかしながら、フッ素樹脂系塗料は耐汚染性、な
かんづく常乾型塗膜は耐ダートコレクション性を欠くこ
とから美観性の低下を招き、耐摩耗性、耐溶剤性も不十
分である。また、アクリルシリコン系塗料は付着性、耐
ダートコレクション性においては前者より優れている
が、耐候性についてはさらに向上が望まれている。2. Description of the Related Art In the field of coating materials, improvement of weather resistance has become an important issue especially when applied to outdoor structures. Heretofore, fluororesin-based paints, acrylic silicone-based paints and the like have been known as paints having excellent weather resistance. However, fluororesin-based paints have stain resistance, and normally dry coatings lack dart collection resistance, resulting in poor aesthetics, and insufficient abrasion resistance and solvent resistance. Further, the acrylic silicone-based paint is superior to the former in adhesiveness and dirt collection resistance, but further improvement in weather resistance is desired.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、耐候
性、耐汚染性、なかんづく耐ダートコレクション性、諸
基材に対する付着性等に優れた塗料組成物を提供するこ
とにある。An object of the present invention is to provide a coating composition excellent in weather resistance, stain resistance, especially dirt collection resistance, adhesion to various substrates and the like.
【０００４】[0004]
【課題を解決するための手段】本発明は、（Ａ）ヒンダ
ードアミン系光安定基を有するアクリル樹脂 ６０〜９
９重量部
（Ｂ）シランカップリング剤 １〜４０重量部および
（Ｃ）無黄変タイプのポリイソシアネート １５〜２０
０重量部を配合してなる塗料組成物に係る。The present invention provides (A) an acrylic resin having a hindered amine-based photostable group 60 to 9
9 parts by weight (B) silane coupling agent 1 to 40 parts by weight and (C) non-yellowing type polyisocyanate 15 to 20
The present invention relates to a coating composition containing 0 part by weight.
【０００５】[0005]
【発明の実施の形態】本発明に用いる塗料組成物におい
て、（Ａ）ヒンダードアミン系光安定基を有するアクリ
ル樹脂としては、側鎖及び／又は主鎖にヒンダードアミ
ン系光安定基を有するアクリル樹脂を適宜用いることが
でき、具体例としては重合性ヒンダードアミン系光安定
性単量体０.１〜３０重量％と酸性官能基含有重合性単
量体０.１〜３０重量％、アクリル酸エステル又はメタ
クリル酸エステル４０〜９９.８重量％を共重合させて
なるアクリル樹脂若しくはこれらに更に他の重合性単量
体を共重合させてなるアクリル樹脂を例示できる。BEST MODE FOR CARRYING OUT THE INVENTION In the coating composition used in the present invention, the acrylic resin having a hindered amine light-stabilizing group (A) is an acrylic resin having a hindered amine light-stabilizing group in the side chain and / or main chain. As a specific example, a polymerizable hindered amine light-stable monomer 0.1 to 30% by weight and an acidic functional group-containing polymerizable monomer 0.1 to 30% by weight, an acrylic acid ester or methacrylic acid can be used. Examples thereof include an acrylic resin obtained by copolymerizing 40 to 99.8% by weight of an ester, or an acrylic resin obtained by further copolymerizing these with another polymerizable monomer.
【０００６】重合性ヒンダードアミン系光安定性単量体
の具体例としては、４−（メタ）アクリロイルオキシ−
２,２,６,６−テトラメチルピペリジン、４−（メタ）
アクリロイルオキシ−１,２,２,６,６−ペンタメチルピ
ペリジン、４−（メタ）アクリロイルアミノ−２,２,
６,６−テトラメチルピペリジン等を例示できる。また
市販のヒンダードアミン系光安定剤若しくはこれらにビ
ニル基のような重合性官能基を置換したものも適宜用い
ることができ、斯かる市販のヒンダードアミン系光安定
剤の具体例としてはアデカスタブＬＡ−８２、アデカス
タブＬＡ−８７（旭電化株式会社製）、Ｓanol ＬＳ−
７７０（三共株式会社製）等を例示できる。Specific examples of the polymerizable hindered amine light-stable monomer include 4- (meth) acryloyloxy-
2,2,6,6-tetramethylpiperidine, 4- (meth)
Acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-2,2,
Examples include 6,6-tetramethylpiperidine and the like. Further, commercially available hindered amine light stabilizers or those in which a polymerizable functional group such as a vinyl group is substituted can also be appropriately used, and specific examples of such commercially available hindered amine light stabilizers include ADEKA STAB LA-82, ADEKA STAB LA-87 (Asahi Denka Co., Ltd.), Sanol LS-
770 (manufactured by Sankyo Co., Ltd.) and the like.
【０００７】酸性官能基含有重合性単量体としては、ア
クリル酸、メタクリル酸、クロトン酸、イタコン酸、マ
レイン酸等のカルボキシル基含有単量体、ビニルスルホ
ン酸、スチレンスルホン酸等のスルホン酸含有単量体を
例示できる。アクリル酸エステル又はメタクリル酸エス
テルとしては、メチル（メタ）アクリレート、エチル
（メタ）アクリレート、プロピル（メタ）アクリレー
ト、ブチル（メタ）アクリレート、ラウリル（メタ）ア
クリレート、ステアリル（メタ）アクリレート、シクロ
ヘキシル（メタ）アクリレート等を例示でき、これらは
一種又は二種以上を用いることができる。これらと共重
合させてもよい他の重合性単量体としては、スチレン、
酢酸ビニル等のビニル系単量体、グリシジル（メタ）ア
クリレート等のエポキシ系単量体等を例示できる。これ
ら単量体を共重合させて本発明の（Ａ）成分を製造する
方法としては、２,２−アゾビスイソブチロニトリル、
２,２−アゾビス−２−メチルブチロニトリル、２,２'
−アゾビス−２,４−ジメチルバレロニトリル、ベンゾ
イルパーオキサイド等の重合開始剤を単量体の合計重量
に対して０.０１〜２０重量部添加し、室温から２２０
℃程度の温度で重合反応させることにより製造できる。
重合は、乳化、懸濁、溶液、塊状等各種の方法で行うこ
とができる。重合に際しては分子量や重合状態の調節を
目的としてラウリルメルカプタン等の重合調節剤を併用
してもよい。本発明の（Ａ）成分は、そのまま、もしく
は水又は有機溶媒等の各種溶媒に溶解させて用いること
ができる。有機溶媒としてはトルエン、キシレン等を例
示することができる。The acidic functional group-containing polymerizable monomer includes a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, and a sulfonic acid such as vinyl sulfonic acid and styrene sulfonic acid. A monomer can be illustrated. Examples of acrylic acid ester or methacrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate. An acrylate etc. can be illustrated and these can use 1 type (s) or 2 or more types. Other polymerizable monomers that may be copolymerized with these, styrene,
Examples thereof include vinyl-based monomers such as vinyl acetate and epoxy-based monomers such as glycidyl (meth) acrylate. As a method for producing the component (A) of the present invention by copolymerizing these monomers, 2,2-azobisisobutyronitrile,
2,2-azobis-2-methylbutyronitrile, 2,2 '
-Azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, and other polymerization initiators are added in an amount of 0.01 to 20 parts by weight based on the total weight of the monomers, and the temperature is adjusted to 220 from room temperature.
It can be produced by carrying out a polymerization reaction at a temperature of about ° C.
The polymerization can be carried out by various methods such as emulsification, suspension, solution and lump. In the polymerization, a polymerization regulator such as lauryl mercaptan may be used together for the purpose of controlling the molecular weight and the polymerization state. The component (A) of the present invention can be used as it is or after being dissolved in various solvents such as water or an organic solvent. Examples of organic solvents include toluene and xylene.
【０００８】本発明に用いることのできる（Ｂ）シラン
カップリング剤としては、分子中にトリメトキシシラン
基やトリエトキシシラン基等の加水分解性シラン基とビ
ニル基、アミノ基、エポキシ基等の有機官能基を有する
化合物より適宜選択することができ、これらはオリゴマ
ーであってもよい。中でもエポキシ基を有するシランカ
ップリング剤が被膜強度の点から好ましく、その具体例
としては、３−グリシドキシプロピルトリメトキシシラ
ン（ＳiＯ2：２５.４％）及びそのオリゴマー、３−グ
リシドキシプロピルメチルジエトキシシラン（ＳiＯ2：
２４.２％）、２−（３,４−エポキシシクロヘキシル）
エチルトリメトキシシラン（ＳiＯ2：２４.４％）等を
例示できる。（Ｂ）成分は（Ａ）成分１００重量部に対
して通常１〜４０重量部、好ましくは２〜２０重量部の
割合で配合するのが好ましい。As the silane coupling agent (B) which can be used in the present invention, a hydrolyzable silane group such as trimethoxysilane group or triethoxysilane group and a vinyl group, an amino group, an epoxy group or the like are contained in the molecule. It can be appropriately selected from compounds having an organic functional group, and these may be oligomers. Among them, a silane coupling agent having an epoxy group is preferable from the viewpoint of film strength, and specific examples thereof include 3-glycidoxypropyltrimethoxysilane (SiO 2 : 25.4%) and its oligomer, 3-glycidoxy. Propylmethyldiethoxysilane (SiO 2 :
24.2%), 2- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane: it may be exemplified (SiO 2 24.4%) and the like. The component (B) is usually added in an amount of 1 to 40 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the component (A).
【０００９】本発明に用いることのできる（Ｃ）無黄変
タイプのポリイソシアネートとしては、脂肪族系のポリ
イソシアネートを広く用いることができ、中でもヘキサ
メチレンジイソシアネートもしくはヘキサメチレンジイ
ソシアネートの誘導体を好ましく用いることができる。
また、イソシアネート化合物と水、エチレングリコー
ル、ジエチレングリコール、１,３−ブチレングリコー
ル、ジプロピレングリコール、ネオペンチルグリコー
ル、グリセリン、イソホロンジアミン、ヘキサメチレン
ジアミン等の低分子量多官能化合物との反応によって得
られる化合物であってもよい。例えば、ヘキサメチレン
ジイソシアネートと水とを反応させて得られる化合物等
を好ましく用いることができる。As the (C) non-yellowing type polyisocyanate which can be used in the present invention, aliphatic polyisocyanates can be widely used, and among them, hexamethylene diisocyanate or a derivative of hexamethylene diisocyanate is preferably used. You can
A compound obtained by reacting an isocyanate compound with low molecular weight polyfunctional compounds such as water, ethylene glycol, diethylene glycol, 1,3-butylene glycol, dipropylene glycol, neopentyl glycol, glycerin, isophoronediamine, and hexamethylenediamine. It may be. For example, a compound obtained by reacting hexamethylene diisocyanate with water can be preferably used.
【００１０】また、イソシアネート基は極めて反応性が
高いため保存中に反応劣化を生じ易く、また本発明の各
成分を予め混合した組成物は、直ちに硬化を開始するた
め保存に適さないという問題点を有する。斯かる問題点
は（Ｃ）成分のみ施工の直前に混合するなど多液型の塗
料とすることで解消し得るが、更に利便性の高い方法と
してフェノール、アミン、アルコール、ラクタム類等の
ブロック剤でイソシアネート基をマスクし、安定化させ
る方法がある。斯かるブロック剤の具体例としては、低
級アルコール類、フェノール、クレゾール等のフェノー
ル類、メチルセロソルブ等の水酸基含有エーテル類、乳
酸アミル等の水酸基含有エステル類、ブチルメルカプタ
ン等のメルカプタン類、アセトアニリド等の酸アミド
類、ε−ラクタム等のラクタム類等を挙げることができ
る。これらのブロック剤を必要により触媒の存在下でイ
ソシアネート化合物と６０〜１８０℃程度の温度で２〜
１０時間反応させることによりイソシアネート化合物の
安定化を図ることができる。尚、（Ｃ）成分としてイソ
シアネート基のマスクされたものを用いる場合は、施工
時に１４０℃以上に加温し、ブロック剤を解離させて活
性イソシアネート基を再生する工程を設ける。（Ｃ）成
分は（Ａ）成分 １００重量部に対して通常１５〜２０
０重量部、好ましくは２５〜１５０重量部の割合で配合
するのが好ましい。Further, since the isocyanate group is extremely reactive, reaction deterioration is likely to occur during storage, and the composition in which each component of the present invention is premixed is not suitable for storage because it immediately starts curing. Have. Although such a problem can be solved by using a multi-liquid type paint such as mixing only the component (C) immediately before the construction, a more convenient method is to block the phenol, amine, alcohol, lactams and the like. There is a method for stabilizing the isocyanate group by masking with. Specific examples of such blocking agents include lower alcohols, phenol, phenols such as cresol, hydroxyl group-containing ethers such as methyl cellosolve, hydroxyl group-containing esters such as amyl lactate, mercaptans such as butyl mercaptan, and acetanilide. Examples thereof include acid amides and lactams such as ε-lactam. If necessary, these blocking agents may be added to the isocyanate compound in the presence of a catalyst at a temperature of about 60 to 180 ° C. for 2 to 2
By reacting for 10 hours, the isocyanate compound can be stabilized. When a component having a masked isocyanate group is used as the component (C), a step of heating at 140 ° C. or higher to dissociate the blocking agent to regenerate the active isocyanate group is provided. The component (C) is usually 15 to 20 relative to 100 parts by weight of the component (A).
It is preferable to add 0 parts by weight, preferably 25 to 150 parts by weight.
【００１１】本発明の塗料組成物は、（Ｄ）成分である
ベンゾトリアゾール系、シアノアクリレート系、ベンゾ
フェノン系又はサリチル酸系紫外線吸収剤を配合するこ
とにより相乗的な耐候性向上効果があり、中でもベンゾ
トリアゾール系紫外線吸収剤を配合した場合にその効果
が著しい。ベンゾトリアゾール系の紫外線吸収剤として
は例えば２−（２'−ヒドロキシ−５'−メチルフェニ
ル）ベンゾトリアゾール、２−（２'−ヒドロキシ−
３',５'−ジ−ｔ−ブチルフェニル）−５−クロロベン
ゾトリアゾール、２−（２'−ヒドロキシ−５'−イソプ
ロペニルカルボニルオキシエチル）ベンゾトリアゾール
（ＲＵＶＡ−９３）等を、シアノアクリレート系の紫外
線吸収剤としては例えば２−エチルヘキシル−２−シア
ノ−３,３'−ジフェニルアクリレート、エチル−２−シ
アノ−３,３'−ジフェニルアクリレート等を、ベンゾフ
ェノン系の紫外線吸収剤としては例えば２,４−ジヒド
ロキシベンゾフェノン、２−ヒドロキシ−４−オクトキ
シベンゾフェノン、２−ヒドロキシ−４−メトキシベン
ゾフェノン等を、サリチル酸系の紫外線吸収剤としては
例えばフェニルサリシレート、ｐ−ｔｅｒｔ−ブチルフ
ェニルサリシレート、ｐ−オクチルフェニルサリシレー
ト等を挙げることができる。これら紫外線吸収剤は、一
種又は二種以上を同時に配合してもよい。また、これら
の紫外線吸収剤は、各種樹脂と重合させて配合すること
もでき、また、その単量体を（Ａ）成分のアクリル樹脂
に共重合させて用いることもできる。（Ｄ）成分の配合
量は本発明の塗料組成物１００重量部に対し、０.１〜
３重量部とするのが好ましい。更に本発明の塗料組成物
には（Ｅ）成分である酸化セリウムを配合することによ
り一層の耐候性向上効果を付与し得る。（Ｅ）成分の配
合量は本発明の塗料組成物１００重量部に対し、０.１
〜１０重量部とするのが好ましい。本発明の塗料組成物
には前記各成分に加えて必要に応じてポリエステルポリ
オール、ダイマー酸変性エポキシ樹脂等の成分を配合す
ることができ、被膜硬度や耐ひっかき傷性の向上、柔軟
性の改善等を図ることができる。The coating composition of the present invention has a synergistic weather resistance-improving effect by incorporating a benzotriazole-based, cyanoacrylate-based, benzophenone-based or salicylic acid-based UV absorber which is the component (D). The effect is remarkable when a triazole-based ultraviolet absorber is added. Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-).
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-isopropenylcarbonyloxyethyl) benzotriazole (RUVA-93) and the like are cyanoacrylate-based. Examples of the ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate, and examples of the benzophenone-based ultraviolet absorber include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like are used as salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl. Can include salicylates, etc. It These UV absorbers may be used alone or in combination of two or more. Further, these ultraviolet absorbers can be blended by polymerizing with various resins, or the monomer thereof can be used by copolymerizing with the acrylic resin of the component (A). The blending amount of the component (D) is 0.1 to 100 parts by weight of the coating composition of the present invention.
It is preferably 3 parts by weight. Further, by adding cerium oxide as the component (E) to the coating composition of the present invention, a further effect of improving weather resistance can be imparted. The compounding amount of the component (E) is 0.1 with respect to 100 parts by weight of the coating composition of the present invention.
It is preferably 10 to 10 parts by weight. In addition to the above components, the coating composition of the present invention can be blended with components such as polyester polyol and dimer acid-modified epoxy resin, if necessary, to improve coating hardness and scratch resistance, and improve flexibility. And so on.
【００１２】本発明の塗料組成物には、意匠性や視認性
の向上のために各種染料や顔料を、難燃性の付与のため
に難燃剤を、防錆性を付与するため亜鉛、リン酸アルミ
ニウム、芳香族一塩基酸、アミノカルボン酸類等の防錆
剤を、菌やかびによる被膜劣化防止のため銀系、ゼオラ
イト系、第４級アンモニウム塩系等の抗菌剤、抗かび剤
等をそれぞれ配合してもよく、これらの他、本発明の目
的を損なわない範囲で分散湿潤剤、硬化促進剤、脱泡剤
等の添加剤を適宜配合することができる。The coating composition of the present invention contains various dyes and pigments for improving design and visibility, a flame retardant for imparting flame retardancy, and zinc, phosphorus for imparting rust resistance. Antirust agents such as aluminum acid salts, aromatic monobasic acids, aminocarboxylic acids, etc., antibacterial agents such as silver-based, zeolite-based, quaternary ammonium salt-based antifungal agents, etc. to prevent film deterioration due to fungi and mold. Each of them may be blended individually, and in addition to these, additives such as a dispersion wetting agent, a curing accelerator, and a defoaming agent may be blended as appropriate within the range not impairing the object of the present invention.
【００１３】本発明の塗料組成物の製造にあたっては、
特に制限はなく、各成分は同時に、あるいは任意の順序
で配合することができる。また、全部の成分を一時に配
合せずに、一部の成分の配合を塗装の直前に行うことも
できる。斯かる配合は通常の塗料組成物の製造方法に従
って行うことができる。また、必須の成分に加えてジブ
チル錫ジラウレート、ジブチル錫ジアセテートなどの硬
化触媒の配合はもちろん、適宜各種の有機溶媒を用いて
もよく、斯かる有機溶媒の種類や量を調整することによ
り塗料の粘度や乾燥速度を巾広く調整することができ
る。本発明の塗料組成物の目的物への施工にあたって
は、原液のまま、もしくは必要に応じて各種の溶媒で希
釈して、刷毛、ロール刷毛、エアスプレー、エアレスス
プレー、静電塗装、浸漬塗り等任意の方法にて塗装する
ことができる。本発明の塗料組成物の一回の塗り厚は１
０〜１００μm程度とするのが好ましく、適宜重ね塗り
を行うことができるが、無機繊維状物等を配合すること
により一回に数百〜２０００μm程度の塗り厚で塗装す
ることもできる。本発明の塗料組成物は、目的物に塗装
した後、常温または加熱して乾燥させることができる。In producing the coating composition of the present invention,
There is no particular limitation, and the components can be blended simultaneously or in any order. It is also possible to mix some of the components immediately before coating, without mixing all the components at once. Such compounding can be performed according to a usual method for producing a coating composition. Further, in addition to the essential components, dibutyltin dilaurate, dibutyltin diacetate, and the like, as well as the compounding of a curing catalyst, various organic solvents may be appropriately used, and by adjusting the type and amount of such an organic solvent, a coating material is prepared. The viscosity and drying rate of can be widely adjusted. In applying the coating composition of the present invention to an intended product, a stock solution, or diluted with various solvents as necessary, a brush, roll brush, air spray, airless spray, electrostatic coating, dip coating, etc. It can be applied by any method. The coating thickness of the coating composition of the present invention is 1
The thickness is preferably about 0 to 100 μm, and multi-coating can be appropriately performed, but it is also possible to coat with a coating thickness of several hundreds to 2000 μm at a time by blending an inorganic fibrous material or the like. The coating composition of the present invention can be dried at room temperature or by heating after being coated on an object.
【００１４】本発明の塗料組成物は、予め原料中に高価
なアクリル変性シリコン樹脂を配合することなく、ポリ
イソシアネートを媒介として、施工時にアクリル変性シ
リコン樹脂が形成される点が極めてユニークであり、斯
かる作用により、
（１）他の成分との分散性の改善
（２）顔料配合による塗膜への悪影響の軽減
（３）溶媒使用削減による環境負荷の軽減
（４）塗膜物性の向上
（５）省資源といった優れた効果を有する。
また本発明の塗料組成物によればヒンダードアミン系光
安定剤とシランカップリング剤の相乗効果により、従来
にない優れた耐候性を有する塗膜が得られるため、屋外
各種構造物の超長期防食、耐候性被覆用途に好適であ
る。即ち、本発明の塗料組成物は、柔軟性、耐屈曲性、
硬度、付着性、耐汚染性、耐食性、保色性、耐候性、耐
熱性等に優れ、コンクリート、セラミックス、セメン
ト、ＦＲＰ、木材、プラスチックス、ガラス、金属等の
各種の基材に対し優れた被膜効果を有する。The coating composition of the present invention is very unique in that the acrylic modified silicone resin is formed at the time of construction by using polyisocyanate as a medium without preliminarily blending the expensive acrylic modified silicone resin in the raw material, Due to such action, (1) improvement of dispersibility with other components (2) reduction of adverse effect on coating film by blending pigment (3) reduction of environmental load by reduction of solvent use (4) improvement of physical properties of coating film ( 5) It has excellent effects such as resource saving. Further, according to the coating composition of the present invention, by the synergistic effect of the hindered amine light stabilizer and the silane coupling agent, it is possible to obtain a coating film having excellent weather resistance that has not been obtained conventionally, ultra long-term corrosion prevention of various outdoor structures, Suitable for weatherproof coating applications. That is, the coating composition of the present invention, flexibility, flex resistance,
Excellent in hardness, adhesion, stain resistance, corrosion resistance, color retention, weather resistance, heat resistance, etc. and excellent for various base materials such as concrete, ceramics, cement, FRP, wood, plastics, glass and metal. Has a coating effect.
【００１５】[0015]
【実施例】以下に実施例を示し、本発明を更に詳細に説
明する。以下において単に部とあるのは重量部を示す。
尚、本発明の各成分のうち、市販品で入手可能なものを
以下に紹介する。本発明の成分（Ａ）として用いること
のできるヒンダードアミン系光安定剤を有するアリル樹
脂としては、ユーダブルＳ−２８１８、同Ｈ−４８１８
〔（株）日本触媒製〕を例示できる。本発明の（Ｂ）成
分として用いることのできるシランカップリング剤とし
ては、ＫＢＭ−４０３（３−グリシドキシプロピルトリ
メトキシシラン）、ＫＢＥ−４０２（３−グリシドキシ
プロピルメチルジエトキシシラン）、ＫＢＭ−３０３
〔２−（３,４−エポキシシクロヘキシル）エチルトリ
メトキシシラン〕（以上いずれも信越化学工業株式会社
製）、ＭＳ５１０１（３−グリシドキシプロピルトリメ
トキシシランのオリゴマー チッソ株式会社製）を例示
できる。The present invention will be described in more detail with reference to the following examples. In the following, "parts" means "parts by weight".
Among the components of the present invention, commercially available products will be introduced below. Examples of the allyl resin having a hindered amine-based light stabilizer that can be used as the component (A) of the present invention include Udouble S-2818 and H-4818.
An example is [manufactured by Nippon Shokubai Co., Ltd.]. Examples of the silane coupling agent that can be used as the component (B) of the present invention include KBM-403 (3-glycidoxypropyltrimethoxysilane), KBE-402 (3-glycidoxypropylmethyldiethoxysilane), KBM-303
Examples include [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] (all manufactured by Shin-Etsu Chemical Co., Ltd.) and MS5101 (oligomer of 3-glycidoxypropyltrimethoxysilane manufactured by Chisso Corporation).
【００１６】（Ｃ）成分に用いることのできる無黄変タ
イプのイソシアネート化合物としては、コロネートＨ
Ｘ、コロネートＨＫ、コロネートＲ３０１、コロネート
２０９４、コロネートＮ、コロネートＨＬ（ＮＣＯ含量
１３.２％）、コロネートＨＬ−１００（ＮＣＯ含量１
７.１％）（以上日本ポリウレタン工業株式会社製）、
バーノックＤＮ９９３−７５Ｘ（大日本インキ化学工業
株式会社製）等を例示できる。また、コロネートＥＸ
（ＮＣＯ含量２１.２％ 日本ポリウレタン工業株式会
社製）等の３量体も好ましく用いることができる。イソ
シアネート基がマスクされ安定化された（Ｃ）成分のう
ち、市販品としては、コロネート２５０７、コロネート
２５１３、コロネートＡＰステープル（以上、日本ポリ
ウレタン工業株式会社製）、バーノックＢ３−８６７
（大日本インキ化学工業株式会社製）等を好ましく用い
ることができる。Coronate H is a non-yellowing type isocyanate compound which can be used as the component (C).
X, Coronate HK, Coronate R301, Coronate 2094, Coronate N, Coronate HL (NCO content 13.2%), Coronate HL-100 (NCO content 1
7.1%) (all manufactured by Nippon Polyurethane Industry Co., Ltd.),
Burnock DN993-75X (made by Dainippon Ink and Chemicals, Inc.) etc. can be illustrated. Also, Coronate EX
A trimer such as (NCO content 21.2% manufactured by Nippon Polyurethane Industry Co., Ltd.) can also be preferably used. Among the (C) components whose isocyanate groups have been masked and stabilized, as commercially available products, Coronate 2507, Coronate 2513, Coronate AP staple (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Vernock B3-867 are available.
(Manufactured by Dainippon Ink and Chemicals, Inc.) and the like can be preferably used.
【００１７】（Ｄ）成分として用いることのできる紫外
線吸収剤としてはＰＵＶＡ−３０Ｍ（メタクリル酸メチ
ルとＲＵＶＡ−９３との共重合体）（大塚化学株式会社
製）、ザロール（ダウ・ケミカル社製、フェニルサリシ
レート）、スミソーブ−９０（住友化学工業株式会社
製、ｐ−ｔｅｒｔ−ブチルフェニルサリシレート）、Ａ
ＳＬ−２３（湘南化学株式会社製、２,４−ジヒドロキ
シベンゾフェノン）、シーソーブ−７０１（白石カルシ
ウム株式会社製）、Ｕvinul−Ｎ−５３９（ＢＡＳＦ社
製、２−エチルヘキシル−２−シアノ−３,３'−ジフェ
ニルアクリレート）、また（Ｅ）成分として用いること
のできる酸化セリウム系紫外線吸収剤としてはニードラ
ールＷ−１００、ニードラールＵ−１００（多木化学株
式会社製）等を例示できる。As the ultraviolet absorber which can be used as the component (D), PUVA-30M (copolymer of methyl methacrylate and RUVA-93) (manufactured by Otsuka Chemical Co., Ltd.), Zalor (manufactured by Dow Chemical Co., Phenyl salicylate), Sumisorb-90 (Sumitomo Chemical Co., Ltd., p-tert-butylphenyl salicylate), A
SL-23 (Shonan Chemical Co., Ltd., 2,4-dihydroxybenzophenone), Seesorb-701 (Shiraishi Calcium Co., Ltd.), Uvinul-N-539 (BASF, 2-ethylhexyl-2-cyano-3,3). '-Diphenyl acrylate), and examples of the cerium oxide-based ultraviolet absorber that can be used as the component (E) include Nedral W-100 and Nedral U-100 (manufactured by Taki Chemical Co., Ltd.).
【００１８】実施例及び比較例
表１〜５に記載の成分及びこれに溶剤、触媒、分散剤、
消泡剤、ゲル化剤、紫外線吸収剤を配合し、実施例及び
比較例の塗料組成物を作製した。表中の各成分の割合は
固形分換算重量部を示す。Examples and Comparative Examples Ingredients listed in Tables 1 to 5 and solvents, catalysts, dispersants,
An antifoaming agent, a gelling agent, and an ultraviolet absorber were blended to prepare coating compositions of Examples and Comparative Examples. The ratio of each component in the table indicates parts by weight in terms of solid content.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【表３】 [Table 3]
【００２２】[0022]
【表４】 [Table 4]
【００２３】[0023]
【表５】 [Table 5]
【００２４】
＊１ 大塚化学株式会社製 チタン酸カリウム繊維
＊２ テイカ株式会社製
＊３，４ 白石工業株式会社製
＊５ 土屋カオリン株式会社製
＊６，７ 東洋アルミニウム株式会社製
＊８ 日本黒鉛工業株式会社製
＊９ 日本ユニカー株式会社製
＊１０ 松本製薬工業株式会社製 メチルシリルトリ
イソシアネート
＊１１ 松本製薬工業株式会社製 テトライソシアネ
ートシラン* 1 Otsuka Chemical Co., Ltd. potassium titanate fiber * 2 Teika Co., Ltd. * 3, 4 Shiraishi Industry Co., Ltd. * 5 Tsuchiya Kaolin Co., Ltd. * 6, 7 Toyo Aluminum Co., Ltd. * 8 Nippon Graphite Industry Co., Ltd. Co., Ltd. * 9 Nippon Unicar Co., Ltd. * 10 Matsumoto Pharmaceutical Co., Ltd. methylsilyltriisocyanate * 11 Matsumoto Pharmaceutical Co., Ltd. tetraisocyanate silane
【００２５】実施例の上塗用１においては、コロネート
ＥＸ以外の成分をポリビーカーに採取し、小型デイスパ
ーで約１０分間撹拌、次いでコロネートＥＸを加えて、
引き続き小型デイスパーで、更に５分間撹拌することに
より調製した。同様にして実施例２及び３を調製した。In Topcoating 1 of the example, the ingredients other than Coronate EX were sampled in a polybeaker and stirred with a small disper for about 10 minutes, then Coronate EX was added,
It was then prepared by stirring with a small disper for an additional 5 minutes. Examples 2 and 3 were similarly prepared.
【００２６】実施例４および５の場合には、コロネート
の配合までは実施例１に準じて調製、実施例４において
はＰＵＶＡ−３０Ｍを、実施例５においてはＰＵＶＡ−
３０Ｍ及びニードラールＷ−１００を加えて、小型ディ
スパーで約５分間撹拌して調製し、主剤とした。実施例
の加熱乾燥型の場合には、成膜のためのイソシアネート
としてブロック型を使用するので長期貯蔵にも耐える
が、常温乾燥型の場合には長期貯蔵できない。従って両
者をイソシアネート（架橋剤）と主剤（他の混合物）の
二つに分けて貯蔵し、使用の際所定の割合で混合する必
要がある。実施例６および７においては、コロネート以
外の各成分をポリビーカーに採取し、ペースト状にした
後小型３本ロールミルで２回ローリングし、得られた混
練物を小型ディスパーで約５分間撹拌し、主剤とした。
使用の際コロネートＥＸと所定の割合で混合した。実施
例２０においてはコロネートおよびアルミペースト１９
００Ｍ以外の各成分をポリビーカーに採取し、ペースト
状にした後、小型３本ロールミルで２回ローリングし、
得られた混練物にアルミペースト１９００Ｍを加えて小
型ディスパーで約５分間撹拌し、主剤とした。使用の際
コロネートＲ３０１と所定の割合で混合した。In the case of Examples 4 and 5, preparation was carried out in accordance with Example 1 up to the addition of coronate, PUVA-30M was used in Example 4, and PUVA-M was used in Example 5.
30M and Nidral W-100 were added, and the mixture was stirred with a small disper for about 5 minutes to prepare a main agent. In the case of the heat-drying type of the example, since the block type is used as the isocyanate for film formation, it can withstand long-term storage, but the room-temperature drying type cannot store it for a long time. Therefore, it is necessary to separately store both the isocyanate (crosslinking agent) and the main agent (other mixture), and mix them at a predetermined ratio at the time of use. In Examples 6 and 7, each component other than coronate was collected in a polybeaker, made into a paste, and then rolled twice with a small three-roll mill, and the resulting kneaded product was stirred with a small disper for about 5 minutes, Used as the main ingredient.
At the time of use, it was mixed with Coronate EX at a predetermined ratio. In Example 20, coronate and aluminum paste 19
Collect each component other than 00M into a poly beaker, make a paste, and roll twice with a small three-roll mill,
Aluminum paste 1900M was added to the obtained kneaded product, and the mixture was stirred with a small disper for about 5 minutes to prepare a main agent. At the time of use, it was mixed with Coronate R301 at a predetermined ratio.
【００２７】実施例２１はコロネートＥＸを除いて全成
分を容器に採取し、小型ディスパーで約２０分間撹拌す
ることにより調製し、主剤とした。使用の際コロネート
ＥＸと所定の割合で混合した。実施例８においては全成
分を容器に採取し、約１０分間小型ディスパーで撹拌し
調製した。実施例９においては、ＰＵＶＡ−３０Ｍを除
く全成分を容器に採取、実施例８に準じて撹拌、次いで
ＰＵＶＡ−３０Ｍを加えて、更に５分間撹拌をして調製
した。Example 21 was prepared by collecting all components except Coronate EX in a container and stirring the mixture with a small disper for about 20 minutes to prepare a main agent. At the time of use, it was mixed with Coronate EX at a predetermined ratio. In Example 8, all the components were collected in a container and stirred for about 10 minutes with a small disper to prepare. In Example 9, all components except PUVA-30M were collected in a container, stirred according to Example 8, and then PUVA-30M was added, followed by stirring for 5 minutes to prepare.
【００２８】実施例１０および１１においてはコロネー
ト２５０７以外の各成分を容器に採取し、ペースト状に
した後、小型３本ロールミルで２回ローリングし、得ら
れた混練物にコロネート２５０７を加え、小型ディスパ
ーで約５分間撹拌し、調製した。実施例２２において
は、コロネート２５０７及びアルミペースト１９００Ｍ
以外の全成分を容器に採取し、ペースト状にした後、小
型３本ロールミルで２回ローリングし、得られた混練物
に、コロネート２５０７及びアルミペースト１９００Ｍ
を加えて、小型ディスパーで約５分間撹拌して、調製し
た。実施例２３においては、バーノックＢ３−８６７を
除く、全成分を容器に採取、小型デイスパーで約２０分
間撹拌、次いでバーノックＢ３−８６７を加えて、更に
約５分間撹拌し、調製した。In Examples 10 and 11, each component other than Coronate 2507 was sampled in a container, made into a paste, and then rolled twice with a small three-roll mill, and Coronate 2507 was added to the resulting kneaded product to obtain a small size. It was prepared by stirring with a disper for about 5 minutes. In Example 22, Coronate 2507 and Aluminum Paste 1900M
All the components except the above were collected into a container, made into a paste, and then rolled twice with a small three-roll mill, and the resulting kneaded product was added to Coronate 2507 and aluminum paste 1900M.
Was added and stirred with a small disper for about 5 minutes to prepare. In Example 23, all components except Vernock B3-867 were collected in a container, stirred with a small disper for about 20 minutes, and then Barnock B3-867 was added and further stirred for about 5 minutes to prepare.
【００２９】比較例
表−４〜５に示す配合からなる比較例の各試料は、実施
例記載の調製方法に準じて調製し、実施例と物性比較を
行った。なお検体はトルエン洗浄した０.３×１５０×
５０mmのブリキ板（ＪＩＳ Ｋ５４１０−２ ）の片面
にハケで２回塗布し作製、常温乾燥型にあっては、室内
で１５日間養生してから次に示す試験を行った。また加
熱乾燥型にあっては、１回エアスプレーし、１５分間セ
ッティング、２回目のエアスプレー後１５分間セッティ
ング、次いで１３０℃で１５分間予熱乾燥を行い、１８
０℃、３０分間の加熱処理を行った。実施例及び比較例
の結果を表６〜９に示す。尚、試験方法は下記によって
行った。Comparative Examples Each sample of Comparative Examples having the formulations shown in Tables 4 to 5 was prepared according to the preparation method described in Examples, and the physical properties were compared with those of Examples. The sample was washed with toluene 0.3 x 150 x
A 50 mm tin plate (JIS K5410-2) was coated twice on one side with a brush to prepare it. In the case of a room temperature dry type, it was cured for 15 days in the room, and then the following test was conducted. For the heat-drying type, air spray once, set for 15 minutes, set for 15 minutes after the second air spray, and then preheat dried at 130 ° C for 15 minutes.
Heat treatment was performed at 0 ° C. for 30 minutes. The results of Examples and Comparative Examples are shown in Tables 6-9. The test method was as follows.
【００３０】貯蔵安定性：１００mlのブリキ製丸缶に各
試料を約８０g入れ、室内で６ケ月間貯蔵し、その間の
経時変化をチェックした。
塗膜の外観：ＪＩＳ Ｋ５４００，６.１
乾燥性：ＪＩＳ Ｋ５４００，６.５
膜厚：マイクロメーターを使用し、測定
耐屈曲性：ＪＩＳ Ｋ ５４００，８.１
硬度：ＪＩＳ Ｋ ５４００，８.４.２
付着性：ＪＩＳ Ｋ ５４００，８.５.２
耐トルエン性：２０℃のトルエン中に１０分間浸漬。
耐沸騰水性：パネルに基板面まで届く切り傷を入れて、
沸騰水中に２時間浸漬。
耐熱性：１８０±５℃に保った熱風循環式加熱炉中で３
時間加熱後、塗膜の黄変度を肉眼で観察、さらにＪＩＳ
Ｋ５４００，８.１の屈曲試験を行った。
耐促進曝露性：デューサイクル Ｗ.Ｏ.Ｍ． １０００
時間照射。塗膜の劣化状態を肉眼で観察、評価した。
耐汚染性：市販事務用マジックインキ黒及び赤、水性マ
ジックペン赤でマーキングし、約１５分間経過後
（Ａ）、約２４時間経過後（Ｂ）、トルエンで拭き取
り、復元状態を観察した。Storage stability: Approximately 80 g of each sample was placed in a 100 ml tin can and stored indoors for 6 months, and the change with time was checked. Appearance of coating film: JIS K5400, 6.1 Drying property: JIS K5400, 6.5 Film thickness: Measured using a micrometer Flex resistance: JIS K 5400, 8.1 Hardness: JIS K 5400, 8.4 .2 Adhesion: JIS K 5400, 8.5. 2 Toluene resistance: Immersed in toluene at 20 ° C. for 10 minutes. Boiling resistance: Put a cut on the panel to reach the substrate surface,
Immerse in boiling water for 2 hours. Heat resistance: 3 in a hot air circulation type heating furnace maintained at 180 ± 5 ℃
After heating for a period of time, the degree of yellowing of the coating film is observed with the naked eye.
A bending test of K5400, 8.1 was conducted. Accelerated exposure resistance: Du Cycle WOM. 1000
Irradiation for hours. The deterioration state of the coating film was visually observed and evaluated. Contamination resistance: Marking was performed with commercially available office magic ink black and red, and water-based magic pen red, and after about 15 minutes (A) and about 24 hours (B), wiped with toluene and the restored state was observed.
【００３１】[0031]
【表６】
＊１：常温乾燥型の場合は主剤のみ、加熱乾燥型の場合
は硬化剤も混合したものである。（以下同様）[Table 6] * 1: In the case of the room temperature dry type, only the main agent is mixed, and in the case of the heat dry type, the curing agent is mixed. (Same below)
【００３２】[0032]
【表７】 [Table 7]
【００３３】[0033]
【表８】
注 ＊２：落砂式摩耗試験 ＪＩＳ Ａ １４５２に準
ず（以下同様）[Table 8] Note * 2: Falling sand type wear test Not according to JIS A 1452 (same below)
【００３４】[0034]
【表９】 [Table 9]
【００３５】試験例１
サンドペーパー＃２４０で研磨、トルエン洗滌した７０
×１５０×０.８mmの鋼板（ＪＩＳ−Ｇ ３１４１ＳＰ
ＣＣ−Ｄ）に実施例の常温乾燥型下塗用Ｎo.２０を１
回、上塗用Ｎo.６及び７それぞれ２回塗りした検体−１
及び２と同様に前処理した鋼板に比較例の下塗用Ｎo.１
２１を１回、上塗用Ｎo.１０３を２回塗装した検体３を
作製、さらに同様に前処理した鋼板に市販アクリルシリ
コーン樹脂塗料用プライマー１回、同上塗用白を２回、
いずれも刷毛塗りして作製した検体−４、さらに同様に
前処理した市販変性弗素樹脂塗料下塗１回、同中塗用１
回、同上塗用白１回いずれも刷毛塗りして作製した検体
−５について、各検体とも室内で７日間、常温で養生後
次に示す試験を行った。Test Example 1 Sandpaper # 240 was used to polish and wash with toluene 70
Steel plate of × 150 × 0.8 mm (JIS-G 3141SP
CC-D) with 1 at room temperature dry type undercoating No. 20
No. 6 and No. 7 for top coating 2 times for each sample-1
No. 1 for the undercoat of the comparative example was applied to the steel sheet pretreated in the same manner as
21 is applied once, and No. 103 for overcoating is applied twice, and then a pre-treated steel plate is similarly subjected once with a primer for a commercial acrylic silicone resin paint and twice with white for overcoating.
All were prepared by brush coating Sample-4, and a similar pretreatment of a commercially available modified fluororesin paint undercoat was performed once, and the same intermediate coating was used.
Sample-5, which was prepared by applying a single brush and one white for overcoating, was subjected to the following test after curing at room temperature for 7 days in each sample.
【００３６】[0036]
【表１０】
注 ６０°鏡面光沢度：ＪＩＳ Ｋ５４００ ７.６
耐寒性：−３０℃で３００h放置、取り出し、常温下で
２４h放置後、１０mmφの屈曲テストを行った。[Table 10] Note 60 ° specular gloss: JIS K5400 7.6 Cold resistance: left at −30 ° C. for 300 hours, taken out, left at room temperature for 24 hours, and then subjected to a bending test of 10 mmφ.
【００３７】試験例２
ウエス拭きによって清浄にした７０×１５０×３mmのフ
レキシブル石綿板に実施例の上塗用Ｎo.６を３回刷毛で
塗装し検体−６を、また同様に処理した石綿板に実施例
の上塗用Ｎo.７を３回塗装し、検体−７を作製した。さ
らに上記に準じて比較例の上塗用Ｎo.１０４を３回塗装
して検体−８を得た。なお前出の市販アクリル変性シリ
コン塗料上塗用白を３回刷毛で塗装して検体−９を、さ
らに同様に処理した石綿板に前出の市販変性弗素樹脂塗
料上塗用白を３回刷毛で塗装し、検体−１０を作製し
た。各検体は常温で７日間養生を行った後、次に示す試
験を行った。Test Example 2 A flexible asbestos plate of 70 × 150 × 3 mm which had been cleaned by wiping with a cloth was applied with No. 6 for overcoating of the example by a brush three times, and Sample-6 was applied to the asbestos plate similarly treated. The top coat No. 7 of the example was applied 3 times to prepare a sample-7. Further, in accordance with the above, Sample No. 104 was obtained by applying No. 104 for top coating of the comparative example three times. The above-mentioned commercial acrylic modified silicone paint topcoat white was applied three times with a brush to apply Sample-9, and the asbestos board treated in the same manner was coated with the above-mentioned commercial modified fluororesin paint topcoat white three times with a brush. Then, Sample-10 was prepared. Each specimen was cured at room temperature for 7 days, and then the following test was conducted.
【００３８】[0038]
【表１１】
注３） 耐凍結融解性：ヒートサイクル試験機により−
３０℃３ｈ→５０℃関係湿度９５％（３ｈ）→８０℃関
係湿度６５％（３ｈ）→１７０min→２０℃関係湿度６
５％（１０min）→−３０℃６ｈを１サイクルとして３
０サイクル行い、１０サイクルごとに塗膜の外観と付着
性（２mm角のゴバン目）をテストする。
注４） 各検体をセラスター塗料（株）工場において１
８カ月屋外暴露試験を行い塗膜の汚損状態を肉眼で判定
した。
注５） 原液中の加熱残分：各検体作製に用いた上塗用
の主剤と硬化剤を所定の割合に混合した原液の加熱残分
量をＪＩＳ Ｋ ５４０７ ４により測定した。[Table 11] Note 3) Freeze-thaw resistance: By heat cycle tester-
30 ° C 3h → 50 ° C related humidity 95% (3h) → 80 ° C related humidity 65% (3h) → 170min → 20 ° C related humidity 6
5% (10 min) → -30 ° C 6h as one cycle 3
Perform 0 cycles and test the appearance and adhesion of the coating film (2 mm square edge) every 10 cycles. Note 4) Each sample is 1 at the Caster Star Paint Co., Ltd. factory.
An outdoor exposure test was conducted for 8 months, and the stain state of the coating film was visually judged. Note 5) Heating residue in undiluted solution: The amount of undiluted heating solution of the undiluted solution prepared by mixing the main agent for overcoating and the curing agent used in the preparation of each sample in a predetermined ratio was measured in accordance with JIS K54074.
【００３９】試験例３
サンドペーパー＃２４０で研磨、トルエン洗滌した７０
×１５０×０.８mmの鋼板に実施例の加熱乾燥型下塗用
Ｎo.２２及び２３をそれぞれ１回エアスプレーし、１５
分間セッティング後、１３０℃１５分間予熱乾燥してか
ら、実施例の上塗用Ｎo.１０及び１１をそれぞれ２回、
エアスプレー（１回スプレー後、１５分間セッティング
して２回目スプレー）１５分間セッティングした後、１
３０℃で１５分間予熱乾燥、次いで１８０℃で３０分間
の加熱乾燥し、検体−１１及び１２を作製した。なお上
記に準じて比較例の下塗用Ｎo.１２２を１回、上塗用Ｎ
o.１０７を２回塗装、同様の加熱乾燥を行って検体−１
３を作製した。更に市販の加熱乾燥型変性フッ素樹脂塗
料についても上述に準じてプライマー１回、中塗用１
回、上塗用１回を塗装、同様に加熱乾燥を行って検体−
１４を作製し、次に示す試験を行った。Test Example 3 Sandpaper # 240 was used to polish and wash with toluene 70
15 × 150 × 0.8 mm steel sheet was air-sprayed once with each of the heat-drying type undercoating Nos. 22 and 23 of the example, and
After setting for 1 minute, preheated and dried at 130 ° C. for 15 minutes, and then No. 10 and 11 for overcoating of the example were respectively applied twice.
Air spray (spray once, set for 15 minutes, then second spray) Set for 15 minutes, then 1
Preheating drying was carried out at 30 ° C. for 15 minutes, and then heating drying was carried out at 180 ° C. for 30 minutes to prepare samples-11 and 12. In addition, according to the above, the undercoating No. 122 of the comparative example was once applied and the topcoating N.
Apply o.107 twice and heat and dry it in the same way.
3 was produced. Further, for a commercially available heat-drying modified fluororesin coating material, one time for the primer and one for the intermediate coating in accordance with the above.
Once, once for top coating, and heat drying in the same way
14 was produced and the following tests were conducted.
【００４０】[0040]
【表１２】 注 耐塩水性：３％食塩水に常温で２４００時間浸漬[Table 12] Note Salt water resistance: Immersed in 3% saline at room temperature for 2400 hours
【００４１】[0041]
【発明の効果】本発明によって、ヒンダードアミン系光
安定基を有するアクリル樹脂にシランカップリング剤及
び無黄変ポリイソシアネート、さらには、特記する紫外
線吸収剤を組み合わせることで、該樹脂の有する超耐候
性能を低下することなく、施工時に容易にシリル化する
ことが可能になり、超耐候性コーティング剤として喧伝
されているフッ素樹脂系コーティング剤に最近指摘さ
れ、問題にされている耐ダートコレクション性にも優
れ、加えて適度にグリシジル基が含まれている故、諸基
材に対する付着性にも優れていることから、現在エポキ
シ樹脂プライマーなどの他種コーティング剤と組み合わ
せ使用されているフッ素樹脂系コーティング剤の複層仕
上げと異なり、同一樹脂を用いたプライマーのみとの組
み合わせで使用できるため、使用材料（主剤、硬化剤、
うすめ液など）の種類も最小限になること、さらに低粘
度のシランカップラーの使用により、低溶剤高固形分化
が可能になるので、大気汚染、人体に対し有害な揮発性
有機成分も大巾にセーブでき、省資源化にも大きく寄与
できることが判った。INDUSTRIAL APPLICABILITY According to the present invention, an acrylic resin having a hindered amine-based light-stabilizing group is combined with a silane coupling agent, a non-yellowing polyisocyanate, and an ultraviolet absorber, which is specially described, to obtain the super weatherability of the resin. It is possible to silylate easily during construction without decreasing the coating performance, and it has been pointed out recently as a fluororesin coating agent that has been proclaimed as a super weather resistant coating agent. Fluorine resin-based coating agent that is currently used in combination with other types of coating agents such as epoxy resin primer because it is excellent and also has excellent adhesion to various substrates because it contains an appropriate amount of glycidyl groups. Unlike the multi-layer finish of, it can be used only in combination with a primer that uses the same resin. Because, using materials (main agent, curing agent,
The amount of thinning liquid etc.) is minimized, and the use of a low-viscosity silane coupler enables low-solvent, high-solidification, so air pollution and volatile organic components harmful to the human body can also be broadened. It was found that it can be saved and can greatly contribute to resource saving.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 泉 美佐夫 大阪府吹田市川岸町10番５号 セラスタ ー塗料株式会社内 (56)参考文献 特開 平６−240200（ＪＰ，Ａ) 特開 平６−287511（ＪＰ，Ａ) 特開 平７−118564（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 5/00 - 201/10 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Misao Izumi 10-5 Kawagishi-cho, Suita City, Osaka Prefecture Celaster Paint Co., Ltd. (56) Reference JP-A-6-240200 (JP, A) JP-A-6 -287511 (JP, A) JP-A-7-118564 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C09D 5/00-201/10
Claims (3)
するアクリル樹脂６０〜９９重量部 （Ｂ）シランカップリング剤 １〜４０重量部および （Ｃ）無黄変タイプのポリイソシアネート １５〜２０
０重量部を配合してなる塗料組成物。1. An acrylic resin having (A) a hindered amine light-stabilizing group, 60 to 99 parts by weight, (B) a silane coupling agent, 1 to 40 parts by weight, and (C) a non-yellowing type polyisocyanate, 15 to 20.
A coating composition containing 0 part by weight.
部に、更に（Ｄ）ベンゾトリアゾール系、シアノアクリ
レート系、ベンゾフェノン系又はサリチル酸系紫外線吸
収剤 ０.１〜３重量部を配合してなる塗料組成物。2. The coating composition according to claim 1, further comprising (D) 0.1 to 3 parts by weight of (D) a benzotriazole-based, cyanoacrylate-based, benzophenone-based or salicylic acid-based UV absorber. Coating composition.
量部に、更に（Ｅ）酸化セリウム ０.１〜１０重量部を
配合してなる塗料組成物。3. A coating composition comprising 100 parts by weight of the coating composition according to claims 1 and 2 and 0.1 to 10 parts by weight of (E) cerium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12330597A JP3516833B2 (en) | 1997-04-24 | 1997-04-24 | Super weather resistant paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12330597A JP3516833B2 (en) | 1997-04-24 | 1997-04-24 | Super weather resistant paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10298493A JPH10298493A (en) | 1998-11-10 |
| JP3516833B2 true JP3516833B2 (en) | 2004-04-05 |
Family
ID=14857260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12330597A Expired - Fee Related JP3516833B2 (en) | 1997-04-24 | 1997-04-24 | Super weather resistant paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3516833B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006335041A (en) * | 2005-06-06 | 2006-12-14 | Matsushita Electric Works Ltd | Substrate material with coating film, manufacturing method of substrate material with coating film, lightening equipment and lamp |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4693966B2 (en) * | 2000-08-11 | 2011-06-01 | セラスター塗料株式会社 | Paint composition |
| JP2005320517A (en) * | 2004-04-06 | 2005-11-17 | Matsushita Electric Works Ltd | Coating composition, substrate with coating film, illuminator and lamp |
| US7884146B2 (en) | 2007-02-20 | 2011-02-08 | Fujifilm Corporation | Polymer material containing ultraviolet absorbent |
| US20100130638A1 (en) | 2007-03-30 | 2010-05-27 | Fujifilm Corporation | Ultraviolet absorbent composition |
| US8039532B2 (en) | 2007-08-16 | 2011-10-18 | Fujifilm Corporation | Heterocyclic compound, ultraviolet absorbent and composition containing the same |
| JP5244437B2 (en) | 2008-03-31 | 2013-07-24 | 富士フイルム株式会社 | UV absorber composition |
| JP5250289B2 (en) | 2008-03-31 | 2013-07-31 | 富士フイルム株式会社 | UV absorber composition |
| JP2009270062A (en) | 2008-05-09 | 2009-11-19 | Fujifilm Corp | Ultraviolet absorbent composition |
| CN114539908A (en) * | 2022-03-18 | 2022-05-27 | 小森新材料科技有限公司 | High yellowing-resistant UV (ultraviolet) photocureable coating applied to decorative sheet and preparation method thereof |
-
1997
- 1997-04-24 JP JP12330597A patent/JP3516833B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006335041A (en) * | 2005-06-06 | 2006-12-14 | Matsushita Electric Works Ltd | Substrate material with coating film, manufacturing method of substrate material with coating film, lightening equipment and lamp |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10298493A (en) | 1998-11-10 |
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