JP4476660B2 - Intermediate coating composition and method for forming laminated coating film - Google Patents
Intermediate coating composition and method for forming laminated coating film Download PDFInfo
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- JP4476660B2 JP4476660B2 JP2004087241A JP2004087241A JP4476660B2 JP 4476660 B2 JP4476660 B2 JP 4476660B2 JP 2004087241 A JP2004087241 A JP 2004087241A JP 2004087241 A JP2004087241 A JP 2004087241A JP 4476660 B2 JP4476660 B2 JP 4476660B2
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- coating composition
- resin
- weight
- coating film
- acid
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Landscapes
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- Paints Or Removers (AREA)
Description
本発明は、自動車車体等の中塗り塗膜を形成する中塗り塗料組成物およびその塗料組成物を用いた積層塗膜の形成方法に関するものである。 The present invention relates to an intermediate coating composition for forming an intermediate coating film of an automobile body or the like and a method for forming a laminated coating film using the coating composition.
自動車用の塗料について、電着塗膜が形成された基材の上に、中塗り塗料、ベース塗料およびクリヤー塗料を、ウェットオンウェットで順次塗装し、塗装された三層を一度に焼付け硬化させる工程（以下、「３コート１ベーク法」という。）で用いる中塗り塗料が、特開２００３−２１１０８５号公報（特許文献１）で提案されている。この３コート１ベーク法は、中塗り塗膜の焼付け乾燥工程、そしてベース塗膜の焼付け乾燥工程が省略されている。このような焼付け乾燥工程の省略は、消費エネルギーおよび塗装工程時間を低減させることができ、経済性および環境面において大きな利点がある。 For automotive coatings, intermediate coating, base coating, and clear coating are sequentially applied wet-on-wet on a substrate on which an electrodeposition coating is formed, and the three layers are baked and cured at once. An intermediate coating material used in the process (hereinafter referred to as “3-coat 1-bake method”) has been proposed in Japanese Patent Application Laid-Open No. 2003-211085 (Patent Document 1). In this three-coat one-bake method, the baking and drying step of the intermediate coating film and the baking and drying step of the base coating film are omitted. The omission of the baking and drying process can reduce energy consumption and coating process time, and has great advantages in terms of economy and environment.
この３コート１ベーク法に用いられる中塗り塗料組成物は樹脂粒子を含み、それによりウェットである中塗り塗膜およびベース塗膜の界面における混層が生じることを低減させている。しかしながら、中塗り塗料中における樹脂粒子の経時での塗料の貯蔵安定性については、十分な検討がなされていなかった。 The intermediate coating composition used in the 3-coat 1-bake method contains resin particles, thereby reducing the occurrence of a mixed layer at the interface between the wet intermediate coating and the base coating. However, sufficient investigation has not been made on the storage stability of the resin particles over time in the intermediate coating.
一般的に、塗料の固形分を高める手法や構造粘性を付与する手法として、樹脂粒子を塗料に含有させる方法がある。しかしながら、これらの樹脂粒子を塗料中に均一に分散することは難しく、例えば、樹脂粒子同士が何らかの理由で反発したり、逆に引き合ったりする現象が起き易い。そのため、これらの樹脂粒子は、塗料中において一見均一に分散しているように見えても、実際は全体あるいは部分的に凝集していることが多い。 In general, as a technique for increasing the solid content of a paint and a technique for imparting structural viscosity, there are methods in which resin particles are contained in the paint. However, it is difficult to uniformly disperse these resin particles in the paint, and for example, a phenomenon in which the resin particles repel each other for some reason or attract each other easily occurs. Therefore, even though these resin particles seem to be uniformly dispersed in the paint, they are actually often aggregated in whole or in part.
すなわち、樹脂粒子を含有する塗料は、製造時には均一に分散し安定性があると思われても、顔料やその他の添加剤等が添加された状態では、貯蔵により徐々に凝集してくる場合があり、粒子の分散状態を安定に維持することは難しい。特に、塗料に熱や剪断力がかかるような状況で使用される塗料は、不安定化が助長され、系内の樹脂粒子が凝集して沈降したり、顔料等の他成分と相互作用を起こし、著しい場合には色相変化まで起こす場合があった。 That is, the coating material containing the resin particles may be uniformly dispersed during production, but may be gradually aggregated by storage in the state where pigments and other additives are added. In addition, it is difficult to stably maintain the dispersed state of the particles. In particular, a paint used in a situation where heat or shear is applied to the paint promotes instability, and the resin particles in the system aggregate and settle, or interact with other components such as pigments. In some cases, the hue change may occur.
特開２００２−２８５０９４号公報（特許文献２）では、ビヒクル、光輝性顔料および塩基性分散剤を含有する光輝性塗料組成物が開示されている。しかしながら、これは光輝性顔料の均一分散化に着目したものであり、本発明のように、中塗り塗料、特に塗料系内の樹脂粒子の貯蔵安定性について検討したものではない。 Japanese Unexamined Patent Application Publication No. 2002-285094 (Patent Document 2) discloses a glittering coating composition containing a vehicle, a glittering pigment, and a basic dispersant. However, this focuses on uniform dispersion of the luster pigment, and does not examine the storage stability of the intermediate coating, particularly the resin particles in the coating system as in the present invention.
一般に塗料組成物としては、貯蔵安定性に優れるものが望まれている。特に、経済性および環境面において大きな利点がある３コート１ベーク法等に用いることができる、機能性の樹脂粒子を含有する中塗り塗料組成物等について、貯蔵安定性に優れたものを提供できるとすれば、使用可能性が広がるため更に利点がある。 In general, a coating composition having excellent storage stability is desired. In particular, an intermediate coating composition containing functional resin particles that can be used in the 3-coat 1-bake method, which has great advantages in terms of economy and environment, can be provided with excellent storage stability. If so, there is a further advantage because the possibility of use is expanded.
本発明は、上記要求を満足させるための中塗り塗料組成物およびその塗料組成物を用いた積層塗膜の形成方法に関し、新規な中塗り塗料組成物を提供することにあり、更に上記塗料組成物を用いた積層塗膜の形成方法を提供することにある。 The present invention relates to an intermediate coating composition for satisfying the above requirements and a method for forming a laminated coating film using the coating composition, and to provide a novel intermediate coating composition, and further to the coating composition. It is providing the formation method of the laminated coating film using a thing.
すなわち、本発明は、
ウレタン変性ポリエステル樹脂（ａ）４０〜５６重量％、
メラミン樹脂（ｂ）１０〜３０重量％、
ブロックイソシアネート化合物（ｃ）１５〜３０重量％、
コアシェル構造を有する非水ディスパージョン樹脂（ｄ）４〜１５重量％
（（ａ）乃至（ｄ）の量は塗料樹脂固形分重量を基準にする。）、および、
塩基性分散剤（ｅ）を塗料固形分重量に対して０．２〜３重量％、
を含有する、中塗り塗料組成物を提供するものであり、これにより上記目的が達成される。
That is, the present invention
Urethane-modified polyester resin (a) 40 to 56% by weight,
Melamine resin (b) 10 to 30% by weight,
Blocked isocyanate compound (c) 15 to 30% by weight,
Non-aqueous dispersion resin (d) having a core-shell structure 4 to 15% by weight
(The amount of (a) to (d) is based on the weight of the solid content of the paint resin), and
0.2 to 3% by weight of the basic dispersant (e) based on the solid weight of the paint,
In this case, the above-mentioned object is achieved.
上記塩基性分散剤（ｅ）は、ポリアクリレート、ポリウレタン、ポリエステルおよびこれらの変性物からなる群から選択される１種以上を主鎖とする高分子であるのが好ましい。また、この塩基性分散剤（ｅ）は、第３級アミノ基、第４級アンモニウムおよび塩基性窒素原子を有する複素環基からなる群から選択される少なくとも一種以上の塩基性基を有するのが好ましい。 The basic dispersant (e) is preferably a polymer having at least one main chain selected from the group consisting of polyacrylates, polyurethanes, polyesters and modified products thereof. The basic dispersant (e) has at least one basic group selected from the group consisting of a tertiary amino group, a quaternary ammonium group, and a heterocyclic group having a basic nitrogen atom. preferable.
また、本発明は、電着塗膜が形成された基材の上に、中塗り塗料組成物、ベース塗料組成物およびクリヤー塗料組成物を、順次塗装する工程、および塗装された三層を一度に焼付け硬化させる工程、を包含する塗膜形成方法であって、
該中塗り塗料組成物が上記中塗り塗料組成物である、積層塗膜の形成方法、も提供する。
The present invention also includes a step of sequentially applying an intermediate coating composition, a base coating composition, and a clear coating composition on a substrate on which an electrodeposition coating film is formed, and three coated layers once. A method of forming a coating film comprising a step of baking and curing,
There is also provided a method for forming a laminated coating film, wherein the intermediate coating composition is the intermediate coating composition.
本発明により、貯蔵安定性に優れた中塗り塗料組成物を提供することができる。この中塗り塗料組成物は、塗装粘度に希釈した状態、すなわち粘度を下げた状態であっても、凝集や沈降を起こさない。この中塗り塗料組成物は色相安定性にも優れるものであり、さらにベース塗膜とクリヤー塗膜とをウェット状態で積層しても混じり合わず、外観が低下したりすることはない。そのため、３コート１ベーク法による積層塗膜を工業的に安定に形成することができる。 According to the present invention, an intermediate coating composition having excellent storage stability can be provided. The intermediate coating composition does not cause aggregation or sedimentation even when diluted to the coating viscosity, that is, when the viscosity is lowered. This intermediate coating composition is excellent in hue stability, and even if the base coating and the clear coating are laminated in a wet state, they do not mix and do not deteriorate in appearance. Therefore, a laminated coating film by the 3-coat 1-bake method can be formed industrially stably.
本発明の中塗り塗料組成物は、ウレタン変性ポリエステル樹脂（ａ）、メラミン樹脂（ｂ）、ブロックイソシアネート化合物（ｃ）、コアシェル構造を有する非水ディスパージョン樹脂（ｄ）、および塩基性分散剤（ｅ）を含有する。 The intermediate coating composition of the present invention comprises a urethane-modified polyester resin (a), a melamine resin (b), a blocked isocyanate compound (c), a non-aqueous dispersion resin (d) having a core-shell structure, and a basic dispersant ( containing e).
ウレタン変性ポリエステル樹脂（ａ）
ウレタン変性ポリエステル樹脂（ａ）は、水酸基含有ポリエステル樹脂と、脂肪族ジイソシアネート化合物とを反応させて得ることができる。
Urethane modified polyester resin (a)
The urethane-modified polyester resin (a) can be obtained by reacting a hydroxyl group-containing polyester resin with an aliphatic diisocyanate compound.
ポリエステル樹脂は一般に、多価カルボン酸および／または酸無水物のような酸成分と多価アルコールを重縮合することによって製造することができる。ウレタン変性ポリエステル樹脂（ａ）の調製に用いられる水酸基含有ポリエステル樹脂は、酸成分中にイソフタル酸を、酸成分の全モル数を基準にして８０モル％以上含有する酸成分を用いて製造される。酸成分中のイソフタル酸の量が８０モル％を下回ると、得られる水酸基含有ポリエステル樹脂のガラス転移点（Ｔｇ）が低くなり、使用に好ましくない。 The polyester resin can generally be produced by polycondensation of an acid component such as a polyvalent carboxylic acid and / or an acid anhydride and a polyhydric alcohol. The hydroxyl group-containing polyester resin used for the preparation of the urethane-modified polyester resin (a) is produced using an acid component containing 80 mol% or more of isophthalic acid in the acid component based on the total number of moles of the acid component. . When the amount of isophthalic acid in the acid component is less than 80 mol%, the glass transition point (Tg) of the resulting hydroxyl group-containing polyester resin is lowered, which is not preferable for use.
水酸基含有ポリエステル樹脂は、４０〜８０℃、好ましくは４５〜７５℃のガラス転移点（Ｔｇ）を有する。上記ガラス転移点（Ｔｇ）が下限を下回ると塗膜硬度が低下し、上限を上回ると耐チッピング性能が低下する。 The hydroxyl group-containing polyester resin has a glass transition point (Tg) of 40 to 80 ° C, preferably 45 to 75 ° C. When the glass transition point (Tg) is below the lower limit, the coating film hardness is lowered, and when it exceeds the upper limit, the chipping resistance is lowered.
水酸基含有ポリエステル樹脂の調製に用いられる酸成分に含まれる、イソフタル酸以外の多価カルボン酸および／または酸無水物は、特に限定されず、例えば、フタル酸、無水フタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロフタル酸、メチルテトラヒドロ無水フタル酸、無水ハイミック酸、トリメリット酸、無水トリメリット酸、ピロメリット酸、無水ピロメリット酸、テレフタル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、アジピン酸、アゼライン酸、セバシン酸、コハク酸、無水コハク酸、ドデセニルコハク酸、ドデセニル無水コハク酸等が挙げられる。 The polyvalent carboxylic acid and / or acid anhydride other than isophthalic acid contained in the acid component used for the preparation of the hydroxyl group-containing polyester resin is not particularly limited. For example, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydro Phthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, terephthalic acid, Examples thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, succinic anhydride, dodecenyl succinic acid, dodecenyl succinic anhydride and the like.
水酸基含有ポリエステル樹脂の調製に用いられる多価アルコールとしては、特に限定されず、例えば、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジオール、２，２−ジメチル−３−ヒドロキシプロピル−２，２−ジメチル−３−ヒドロキシプロピオネート、２，２，４−トリメチル−１，３−ペンタンジオール、ポリテトラメチレンエーテルグリコール、ポリカプロラクトンポリオール、グリセリン、ソルビトール、アンニトール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ヘキサントリオール、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。 The polyhydric alcohol used for the preparation of the hydroxyl group-containing polyester resin is not particularly limited. For example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 2,2-dimethyl-3 -Hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, 2,2,4-trimethyl-1,3-pentanediol, polytetramethylene ether glycol, polycaprolactone polyol, glycerin, sorbitol An'nitoru, trimethylol ethane, trimethylol propane, trimethylol butane, hexanetriol, pentaerythritol, dipentaerythritol and the like.
水酸基含有ポリエステル樹脂の調製において、上記の多価カルボン酸および／または酸無水物、および多価アルコール成分、に加えて、他の反応成分を用いてもよい。このような他の反応成分として、例えば、モノカルボン酸、ヒドロキシカルボン酸、ラクトン等が挙げられる。また、乾性油、反乾性油およびそれらの脂肪酸を用いてもよい。例えば、具体的には、カージュラＥ（シェル化学社製）等のモノエポキサイド化合物、ラクトン類がある。上記ラクトン類は、多価カルボン酸および多価アルコールのポリエステル類へ開環付加してグラフト鎖を形成し得るものであり、例えば、β−プロピオラクロン、ジメチルプロピオラクトン、ブチルラクトン、γ−バレロラクトン、ε−カプロラクトン、γ−カプロラクトン、γ−カプリロラクトン、クロトラクトン、δ−バレロラクトン、δ−カプロラクトン等が挙げられるが、なかでもε−カプロラクトンが最も好ましい。 In the preparation of the hydroxyl group-containing polyester resin, other reaction components may be used in addition to the polyvalent carboxylic acid and / or acid anhydride and the polyhydric alcohol component. Examples of such other reaction components include monocarboxylic acid, hydroxycarboxylic acid, and lactone. Moreover, you may use drying oil, anti-drying oil, and those fatty acids. Specific examples include monoepoxide compounds such as Cardura E (manufactured by Shell Chemical Co.) and lactones. The lactones can be subjected to ring-opening addition to polyesters of polyvalent carboxylic acids and polyhydric alcohols to form graft chains. For example, β-propiolaclone, dimethylpropiolactone, butyllactone, γ- Examples include valerolactone, ε-caprolactone, γ-caprolactone, γ-caprolactone, crotolactone, δ-valerolactone, and δ-caprolactone, among which ε-caprolactone is most preferable.
こうして得られた水酸基含有ポリエステル樹脂と脂肪族ジイソシアネート化合物とを反応させることによって、ウレタン変性ポリエステル樹脂（ａ）が調製される。このような脂肪族ジイソシアネート化合物としては、具体的には、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、シクロヘキサン−１，４−ジイソシアネート、ジシクロヘキシルメタン−４，４−ジイソシアネート、メチルシクロヘキサンジイソシアネートなどを挙げることができる。なかでも、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネートおよびこれらのビュレット体、ヌレート体、アダクト体を用いることが、耐チッピング性能、耐候性の観点から好ましい。 The urethane-modified polyester resin (a) is prepared by reacting the hydroxyl group-containing polyester resin thus obtained with an aliphatic diisocyanate compound. Specific examples of such aliphatic diisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, and methylcyclohexane diisocyanate. . Of these, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and their burettes, nurate bodies, and adduct bodies are preferably used from the viewpoints of chipping resistance and weather resistance.
ウレタン変性ポリエステル樹脂（ａ）の調製においては、水酸基含有ポリエステル樹脂１００重量部に対して脂肪族ジイソシアネート化合物５〜１５重量部を反応させるのが好ましい。ウレタン変性ポリエステル樹脂（ａ）の数平均分子量は、１５００〜３０００であるのが好ましく、１２００〜２５００であるのがさらに好ましい。下限を下回ると塗装作業性および硬化性が十分でなくなる恐れがある。また、上限を上回ると塗装時の不揮発分が低くなりすぎ、かえって作業性が悪くなる。なお、本明細書では、数平均分子量は、スチレンポリマーを標準とするＧＰＣ法により決定される。 In the preparation of the urethane-modified polyester resin (a), it is preferable to react 5 to 15 parts by weight of the aliphatic diisocyanate compound with respect to 100 parts by weight of the hydroxyl group-containing polyester resin. The number average molecular weight of the urethane-modified polyester resin (a) is preferably 1500 to 3000, and more preferably 1200 to 2500. Below the lower limit, the coating workability and curability may be insufficient. On the other hand, when the upper limit is exceeded, the non-volatile content at the time of painting becomes too low, and the workability becomes worse. In the present specification, the number average molecular weight is determined by a GPC method using a styrene polymer as a standard.
また上記ウレタン変性ポリエステル樹脂（ａ）は、３０〜１８０の水酸基価（固形分）を有することが好ましく、４０〜１６０の水酸基価であるのが更に好ましい。上限を上回ると塗膜にした場合の耐水性が低下する恐れがあり、下限を下回ると塗膜の硬化性が低下する恐れがある。また、ウレタン変性ポリエステル樹脂（ａ）の酸価は、３〜３０ｍｇＫＯＨ／ｇ（固形分）であるのが好ましく、更に好ましくは５〜２５ｍｇＫＯＨ／ｇである。上限を上回ると塗膜の耐水性が低下する恐れがあり、下限を下回ると塗膜の硬化性が低下する恐れがある。 The urethane-modified polyester resin (a) preferably has a hydroxyl value (solid content) of 30 to 180, more preferably a hydroxyl value of 40 to 160. If the upper limit is exceeded, the water resistance in the case of a coating film may be reduced, and if the lower limit is exceeded, the curability of the coating film may be reduced. Moreover, it is preferable that the acid value of urethane-modified polyester resin (a) is 3-30 mgKOH / g (solid content), More preferably, it is 5-25 mgKOH / g. If it exceeds the upper limit, the water resistance of the coating film may be lowered, and if it is less than the lower limit, the curability of the coating film may be lowered.
本発明の中塗り塗料組成物中における、上記ウレタン変性ポリエステル樹脂（ａ）の含有量は、塗料樹脂固形分重量を基準にして４０〜５６重量％である。ウレタン変性ポリエステル樹脂（ａ）の含有量が４０重量％を下回ると塗膜にした場合の耐チッピング性能が不十分となる恐れがある。また、含有量が５６重量％を上回ると塗膜にした場合に硬度が低下する恐れがある。含有量は、好ましくは４３〜５０重量％である。 The content of the urethane-modified polyester resin (a) in the intermediate coating composition of the present invention is 40 to 56% by weight based on the weight of the coating resin solid content. If the content of the urethane-modified polyester resin (a) is less than 40% by weight, the chipping resistance when used as a coating film may be insufficient. Moreover, when content exceeds 56 weight%, when it is set as a coating film, there exists a possibility that hardness may fall. The content is preferably 43 to 50% by weight.
メラミン樹脂（ｂ）
メラミン樹脂としては、特に限定されるものではなく、メチル化メラミン樹脂、ブチル化メラミン樹脂あるいはメチルブチル混合型メラミン樹脂を用いることができる。例えば、日本サイテック株式会社から市販されている「サイメル３０３」、「サイメル２５４」、三井東圧株式会社から市販されている「ユーバン１２８」、「ユーバン２０Ｎ６０」、住友化学工業株式会社から市販されている「スミマールシリーズ」等が挙げられる。
Melamine resin (b)
The melamine resin is not particularly limited, and a methylated melamine resin, a butylated melamine resin, or a methylbutyl mixed melamine resin can be used. For example, “Cymel 303” and “Cymel 254” commercially available from Nippon Cytec Co., Ltd., “Uban 128” and “Uban 20N60” commercially available from Mitsui Toatsu Co., Ltd., and commercially available from Sumitomo Chemical Co., Ltd. "Summar series" is listed.
上記メラミン樹脂（ｂ）は、塗料樹脂固形分重量を基準にして１０〜３０重量％含まれる。含有量が下限を下回ると硬化性が不十分となる恐れがあり、上限を上回ると硬化膜が堅くなりすぎ脆くなる恐れがある。メラミン樹脂（ｂ）の含有量は、好ましくは１５〜２５重量％である。 The melamine resin (b) is contained in an amount of 10 to 30% by weight based on the solid weight of the coating resin. If the content is less than the lower limit, the curability may be insufficient, and if the content exceeds the upper limit, the cured film may be too hard and brittle. The content of the melamine resin (b) is preferably 15 to 25% by weight.
ブロックイソシアネート化合物（ｃ）
上記ブロックイソシアネート化合物（ｃ）としては、ヘキサメチレンジイソシアネートあるいはそのヌレート体等の多量体に、活性メチレン基を有する化合物を付加させることによって得られ、加熱によりブロック剤が解離してイソシアネート基が発生し、上記ウレタン変性ポリエステル樹脂中の官能基と反応し硬化するものが挙げられる。上記活性メチレン基を有する化合物としては、アセチルアセトン、アセト酢酸エチル、マロン酸エチルなどの活性メチレン化合物が挙げられる。
Block isocyanate compound (c)
The blocked isocyanate compound (c) is obtained by adding a compound having an active methylene group to a multimer such as hexamethylene diisocyanate or its nurate, and the blocking agent is dissociated by heating to generate an isocyanate group. And those that react with the functional groups in the urethane-modified polyester resin and cure. Examples of the compound having an active methylene group include active methylene compounds such as acetylacetone, ethyl acetoacetate, and ethyl malonate.
上記ブロックイソシアネート化合物の含有量は、塗料樹脂固形分重量を基準にして、１５〜３０重量％である。１７〜２５重量％であることが更に好ましい。上記範囲外では、硬化が不足する。例えば、具体的には旭化成社製活性メチレン型ブロックイソシアネート「デュラネートＭＦ−Ｋ６０Ｘ」等が挙げられる。 The content of the blocked isocyanate compound is 15 to 30% by weight based on the solid weight of the coating resin. More preferably, it is 17 to 25% by weight. Outside the above range, curing is insufficient. Specific examples include active methylene type blocked isocyanate “Duranate MF-K60X” manufactured by Asahi Kasei Corporation.
非水ディスパージョン樹脂（ｄ）
上記コアシェル構造を有する非水ディスパージョン樹脂（ｄ）は、分散安定樹脂と有機溶剤との混合液中で、重合性単量体を共重合させることにより、この混合液に不溶な樹脂粒子として調製することができる。なお「非水ディスパージョン」とは、非水分散型樹脂を意味し、有機溶媒を媒体として樹脂を分散安定化させたものである。
Non-aqueous dispersion resin (d)
The non-aqueous dispersion resin (d) having the core-shell structure is prepared as resin particles insoluble in the mixed solution by copolymerizing a polymerizable monomer in a mixed solution of a dispersion-stable resin and an organic solvent. can do. The “non-aqueous dispersion” means a non-aqueous dispersion type resin, and is obtained by dispersing and stabilizing a resin using an organic solvent as a medium.
非水ディスパージョン樹脂（ｄ）における樹脂粒子は、非架橋樹脂粒子として調製することが好ましい。また、非架橋樹脂粒子を得るため分散安定樹脂の存在下で共重合させる単量体は、ラジカル重合性の不飽和単量体であれば特に制限されない。 The resin particles in the non-aqueous dispersion resin (d) are preferably prepared as non-crosslinked resin particles. The monomer to be copolymerized in the presence of the dispersion-stable resin for obtaining non-crosslinked resin particles is not particularly limited as long as it is a radical polymerizable unsaturated monomer.
但し、上記分散安定樹脂および非水ディスパージョン樹脂（ｄ）の合成において、官能基を有する重合性単量体を用いることが好ましい。官能基を有する非水ディスパージョン樹脂（ｄ）は官能基を含有せしめた分散安定樹脂と共に後記硬化剤と反応して三次元に架橋した塗膜を形成することができるからである。 However, it is preferable to use a polymerizable monomer having a functional group in the synthesis of the dispersion stabilizing resin and the non-aqueous dispersion resin (d). This is because the non-aqueous dispersion resin (d) having a functional group can react with a post-curing agent together with the dispersion stabilizing resin containing the functional group to form a three-dimensionally crosslinked coating film.
分散安定樹脂は、非水ディスパージョン樹脂（ｄ）を有機溶剤中で安定に合成できるものであれば特に限定されるものではない。分散安定樹脂として、具体的には、水酸基価（固形分）が１０〜２５０、好ましくは２０〜１８０であり、酸価（固形分）が０〜１００ｍｇＫＯＨ／ｇ、好ましくは０〜５０ｍｇＫＯＨ／ｇ、数平均分子量が８００〜１０００００、好ましくは１０００〜２００００である、アクリル樹脂、ポリエステル樹脂、ポリエーテル樹脂、ポリカーボネート樹脂またはポリウレタン樹脂等を用いることが好ましい。これらの上限を上回ると樹脂のハンドリング性が低下し、非水ディスパージョン自身のハンドリングも低下する。下限を下回ると塗膜にした場合に樹脂が脱離したり、粒子の安定性が低下したりする。 The dispersion stable resin is not particularly limited as long as it can stably synthesize the non-aqueous dispersion resin (d) in an organic solvent. Specifically, as the dispersion stable resin, the hydroxyl value (solid content) is 10 to 250, preferably 20 to 180, and the acid value (solid content) is 0 to 100 mgKOH / g, preferably 0 to 50 mgKOH / g, It is preferable to use an acrylic resin, a polyester resin, a polyether resin, a polycarbonate resin or a polyurethane resin having a number average molecular weight of 800 to 100,000, preferably 1000 to 20,000. When these upper limits are exceeded, the handling property of the resin is lowered, and the handling of the non-aqueous dispersion itself is also lowered. If the lower limit is not reached, the resin may be detached or the stability of the particles may be reduced when the coating film is formed.
分散安定樹脂の合成方法は、特に限定されるものではないが、ラジカル重合開始剤の存在下でラジカル重合により得る方法、縮合反応や付加反応により得る方法等が好ましいものとして挙げられる。更に、上記分散安定樹脂を得るために用いられる単量体としては、樹脂の特性に応じて適宜選択され得るが、後述する非水ディスパージョンを合成するために用いられる重合性単量体が有するような、水酸基、酸基等の官能基を有するものを用いることが好ましく、更に必要に応じて、グリシジル基、イソシアネート基等の官能基を有するものを用いてもよい。 The method for synthesizing the dispersion stable resin is not particularly limited, and preferred examples include a method obtained by radical polymerization in the presence of a radical polymerization initiator, a method obtained by a condensation reaction or an addition reaction, and the like. Furthermore, the monomer used to obtain the dispersion-stable resin can be appropriately selected according to the properties of the resin, but has a polymerizable monomer used to synthesize a non-aqueous dispersion described later. It is preferable to use those having a functional group such as a hydroxyl group and an acid group, and if necessary, those having a functional group such as a glycidyl group and an isocyanate group may be used.
非水ディスパージョン樹脂（ｄ）は、分散安定樹脂の存在下で重合性単量体を重合させることによって得ることができる。重合性単量体として、ラジカル重合性の単量体を用いることができる。 The non-aqueous dispersion resin (d) can be obtained by polymerizing a polymerizable monomer in the presence of a dispersion stable resin. As the polymerizable monomer, a radical polymerizable monomer can be used.
非水ディスパージョン樹脂（ｄ）の合成に用いられる重合性単量体は、官能基を有するものを用いるのが好ましい。官能基を有する重合性単量体としてその代表的なものは以下のとおりである。水酸基を有する重合性単量体として、例えば、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、メタクリル酸ヒドロキシメチル、アリルアルコール、（メタ）メタクリル酸ヒドロキシエチルとε−カプロラクトンとの付加物等が挙げられる。 As the polymerizable monomer used for the synthesis of the non-aqueous dispersion resin (d), a monomer having a functional group is preferably used. Typical examples of the polymerizable monomer having a functional group are as follows. Examples of the polymerizable monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxymethyl methacrylate, allyl alcohol, and hydroxy (meth) methacrylate. Examples include adducts of ethyl and ε-caprolactone.
一方、酸性基を有する重合性単量体としては、カルボキシル基、スルホン酸基等を有する重合性単量体が挙げられる。カルボキシル基を有するものの例としては、（メタ）アクリル酸、クロトン酸、エタアクリル酸、プロピルアクリル酸、イソプロピルアクリル酸、イタコン酸、無水マレイン酸、フマール酸等が挙げられる。スルホン酸基を有する重合性単量体の例としては、ｔ−ブチルアクリルアミドスルホン酸等が挙げられる。酸性基を有する重合性単量体を用いる場合は、酸性基の一部はカルボキシル基であることが好ましい。 On the other hand, the polymerizable monomer having an acidic group includes a polymerizable monomer having a carboxyl group, a sulfonic acid group, or the like. Examples of those having a carboxyl group include (meth) acrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride, fumaric acid and the like. Examples of the polymerizable monomer having a sulfonic acid group include t-butylacrylamide sulfonic acid. When using the polymerizable monomer which has an acidic group, it is preferable that a part of acidic group is a carboxyl group.
そのほかにも、（メタ）アクリル酸グリシジル等のグリシジル基含有不飽和単量体、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネート、アクリル酸イソシアナトエチル等のイソシアネート基含有不飽和単量体等が、官能基を有する重合性単量体として挙げられる。 In addition, glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate, isocyanate group-containing unsaturated monomers such as m-isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanatoethyl acrylate, etc. Is mentioned as a polymerizable monomer having a functional group.
この他の重合性単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、メタクリル酸トリデシル等の（メタ）アクリル酸アルキルエステル、油脂肪酸とオキシラン構造を有するアクリル酸またはメタクリル酸エステルモノマーとの付加反応物（例えば、ステアリン酸とグリシジルメタクリレートの付加反応物等）、炭素数３以上のアルキル基を含むオキシラン化合物とアクリル酸またはメタクリル酸との付加反応物、スチレン、α−メチルスチレン、ο−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔ−ブチルスチレン、（メタ）アクリル酸ベンジル、イタコン酸エステル（イタコン酸ジメチルなど）、マレイン酸エステル（マイレン酸ジメチルなど）、フマール酸エステル（フマール酸ジメチルなど）、その他に、アクリロニトリル、メタクリロニトリル、メチルイソプロペニルケトン、酢酸ビニル、ベオバモノマー（シェル化学社製、商品名）、ビニルプロピオネート、ビニルピバレート、エチレン、プロピレン、ブタジエン、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、アクリルアミド、ビニルピリジン等の重合性単量体が挙げられる。 Other polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, and n- (meth) acrylate. Butyl, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylic acid alkyl ester such as tridecyl methacrylate, addition reaction product of oil fatty acid and acrylic acid or methacrylic acid ester monomer having oxirane structure (for example, addition reaction product of stearic acid and glycidyl methacrylate), carbon number 3 Oxirane compounds containing the above alkyl groups and acrylic acid or methacrylic acid Addition reaction product of styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, pt-butyl styrene, benzyl (meth) acrylate, itaconic acid ester (dimethyl itaconate, etc.) , Maleic acid esters (such as dimethyl maleate), fumaric acid esters (such as dimethyl fumarate), acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, Veova monomer (made by Shell Chemical Co., Ltd., trade name), vinyl Examples thereof include polymerizable monomers such as propionate, vinyl pivalate, ethylene, propylene, butadiene, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, acrylamide, and vinyl pyridine.
非水ディスパージョン樹脂（ｄ）の調製において、分散安定樹脂と重合性単量体との構成比率は目的に応じて任意に選択できるが、例えば、該両成分の合計重量に基いて分散安定樹脂は３〜８０重量％、特に５〜６０重量％、重合性単量体は９７〜２０重量％、特に９５〜４０重量％が好ましい。さらに有機溶剤中における分散安定樹脂と重合性単量体との合計濃度は合計重量を基準に、３０〜８０重量％、特に４０〜６０重量％が好ましい。 In the preparation of the non-aqueous dispersion resin (d), the constituent ratio of the dispersion stable resin and the polymerizable monomer can be arbitrarily selected according to the purpose. For example, the dispersion stable resin is based on the total weight of the two components. Is preferably 3 to 80% by weight, particularly 5 to 60% by weight, and the polymerizable monomer is preferably 97 to 20% by weight, particularly 95 to 40% by weight. Furthermore, the total concentration of the dispersion stabilizing resin and the polymerizable monomer in the organic solvent is preferably 30 to 80% by weight, particularly 40 to 60% by weight, based on the total weight.
上記非水ディスパージョンを得るための重合反応は、ラジカル重合開始剤の存在下で行うことが好ましい。ラジカル重合開始剤としては、例えば２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系開始剤、ベンゾイルパーオキサイド、ラウリルパーオキサイド、ｔ−ブチルパーオクトエート等が挙げられる。これらの開始剤の使用量は重合性単量体合計１００重量部あたり０．２〜１０重量部、好ましくは０．５〜５重量部が望ましい。分散安定樹脂を含有する有機溶剤中での非水ディスパージョンを得るための重合反応は、一般に６０〜１６０℃程度の温度範囲で約１〜１５時間行うことが好ましい。 The polymerization reaction for obtaining the non-aqueous dispersion is preferably performed in the presence of a radical polymerization initiator. Examples of the radical polymerization initiator include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, Examples include t-butyl peroctoate. These initiators are used in an amount of 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of the polymerizable monomers. In general, the polymerization reaction for obtaining a non-aqueous dispersion in an organic solvent containing a dispersion-stable resin is preferably performed in a temperature range of about 60 to 160 ° C. for about 1 to 15 hours.
こうして得られる非水ディスパージョン樹脂（ｄ）は、水酸基価（固形分）が５０〜４００、好ましくは１００〜３００であり、酸価（固形分）が０〜２００ｍｇＫＯＨ／ｇ、好ましくは０〜５０ｍｇＫＯＨ／ｇ、平均粒径（Ｄ５０）が０．０５〜１０μｍ、好ましくは０．１〜２μｍであるものが好ましい。下限を下回ると粒子形状を維持できず、上限を上回ると塗料組成物に分散した場合の安定性が低下する。 The non-aqueous dispersion resin (d) thus obtained has a hydroxyl value (solid content) of 50 to 400, preferably 100 to 300, and an acid value (solid content) of 0 to 200 mgKOH / g, preferably 0 to 50 mgKOH. / G and an average particle diameter (D50) of 0.05 to 10 μm, preferably 0.1 to 2 μm are preferable. If it is below the lower limit, the particle shape cannot be maintained, and if it exceeds the upper limit, the stability when dispersed in the coating composition is lowered.
また、上記非水ディスパージョンは架橋重合体微粒子と異なり、塗料組成物中においては粒子成分であるが、塗膜においては粒子構造を形成しない特徴を有する。つまり非水ディスパージョンは粒子内に架橋部位が存在しないため、焼き付け過程で粒子形状が変化し、樹脂成分となり得る点が架橋重合体微粒子とは異なる。 Further, the non-aqueous dispersion is different from the crosslinked polymer fine particles, and is a particle component in the coating composition, but has a characteristic that a particle structure is not formed in the coating film. That is, the non-aqueous dispersion is different from the crosslinked polymer fine particles in that there are no cross-linked sites in the particles, so that the particle shape changes during the baking process and can become a resin component.
更に、例えば色材、４８巻（１９７５）第２８頁〜第３４頁中に記載されているＮＡＤ塗料に用いられるＮＡＤ（Ｎｏｎ Ａｑｕｅｏｕｓ Ｄｉｓｐｅｒｓｉｏｎ、非水系重合体分散液）と言われる樹脂粒子も使用することができる。 Furthermore, for example, resin particles called NAD (Non Aqueous Dispersion) used in the NAD paint described in Color Material, Vol. 48 (1975), pages 28 to 34 are also used. be able to.
本発明の中塗り塗料組成物中における、非水ディスパージョン樹脂（ｄ）の含有量は、塗料樹脂固形分重量を基準にして４〜１５重量％である。含有量が下限を下回ると総合塗膜外観が不十分となる恐れがあり、また上限を上回ると耐チッピング性能が低下する恐れがある。この含有量は、好ましくは５〜１２重量％である。 The content of the non-aqueous dispersion resin (d) in the intermediate coating composition of the present invention is 4 to 15% by weight based on the solid weight of the coating resin. If the content is below the lower limit, the overall coating film appearance may be insufficient, and if it exceeds the upper limit, the chipping resistance may be reduced. This content is preferably 5 to 12% by weight.
塩基性分散剤（ｅ）
塩基性分散剤（ｅ）は、塩基性基を有する高分子である。この塩基性分散剤（ｅ）は、ポリアクリレート、ポリウレタン、ポリエステルおよびこれらの変性物からなる群から選ばれる１種以上を主鎖とするものが好ましい。また、塩基性分散剤（ｅ）は、ブロック構造を有していてもよく、またグラフト構造を有していてもよい。特に、ポリウレタンを繰返し単位とするブロックコポリマーを主鎖とするものが、塩基性分散剤（ｅ）としてより好ましい。
Basic dispersant (e)
The basic dispersant (e) is a polymer having a basic group. The basic dispersant (e) preferably has one or more selected from the group consisting of polyacrylates, polyurethanes, polyesters, and modified products thereof as the main chain. Moreover, the basic dispersant (e) may have a block structure or a graft structure. In particular, those having a main chain of a block copolymer having polyurethane as a repeating unit are more preferred as the basic dispersant (e).
上記塩基性分散剤（ｅ）は、第３級アミノ基、第４級アンモニウムおよび塩基性窒素原子を有する複素環基からなる群から選ばれる少なくとも一種以上の塩基性基を有するのが好ましい。そしてこれらの塩基性基は、１分子中に２〜３０００個存在するのが好ましい。下限を下回ると樹脂凝集物の発生の改善の効果が見られない恐れがあり、また上限を超えると、塗膜にした場合の耐水性が低下する恐れがある。塩基性基は、５〜１５００個存在するのがより好ましい。 The basic dispersant (e) preferably has at least one basic group selected from the group consisting of a tertiary amino group, a quaternary ammonium group, and a heterocyclic group having a basic nitrogen atom. And it is preferable that 2-3000 of these basic groups exist in 1 molecule. If the lower limit is not reached, the effect of improving the generation of resin agglomerates may not be seen, and if the upper limit is exceeded, the water resistance in the case of a coating film may be reduced. More preferably, 5 to 1500 basic groups are present.
上記塩基性分散剤は、数平均分子量が１０００〜１００００００であることが好ましい。下限を下回ると塗膜にした場合の耐水性が低下する恐れがあり、上限を上回ると粘度が高すぎて取り扱いが困難となる恐れがある。数平均分子量が２０００〜５０００００であるのがより好ましい。 The basic dispersant preferably has a number average molecular weight of 1,000 to 1,000,000. If it is less than the lower limit, the water resistance in the case of a coating film may be lowered, and if it exceeds the upper limit, the viscosity is too high and handling may be difficult. The number average molecular weight is more preferably 2000 to 500,000.
上記塩基性分散剤（ｅ）としては、市販されているものを使用することもできる。上記市販品としては、例えば、Ｄｉｓｐｅｒｂｙｋ １１０、Ｄｉｓｐｅｒｂｙｋ １６１、Ｄｉｓｐｅｒｂｙｋ １６６、Ｄｉｓｐｅｒｂｙｋ １８２、Ｄｉｓｐｅｒｂｙｋ １８３、Ｄｉｓｐｅｒｂｙｋ １８５（いずれもビックケミー社製）、ソルスパース５０００、ソルスパース２４０００、ソルスパース３２５５０（いずれもアビシア社製）等を挙げることができる。 What is marketed can also be used as said basic dispersing agent (e). Examples of the above-mentioned commercial products include Disperbyk 110, Disperbyk 161, Disperbyk 166, Disperbyk 182, Disperbyk 183, Disperbyk 185 (all manufactured by Big Chemie), Solsperse 5000, Solsperse 24000, and Solsperse 24000, Can be mentioned.
本発明の中塗り塗料組成物は、塩基性分散剤（ｅ）を塗料固形分重量に対して０．２〜３重量％含有する。上限を上回ると、塗膜にした場合の耐水性が低下する恐れがある。また、下限を下回ると添加効果が十分に発揮されない恐れがある。この含有量は、０．４〜２重量％であるのがより好ましい。この塩基性分散剤（ｅ）を中塗り塗料組成物に加えることによって、中塗り塗料組成物の均一分散性および貯蔵時の塗料安定性を向上させることができる。 The intermediate coating composition of the present invention contains the basic dispersant (e) in an amount of 0.2 to 3% by weight based on the solid content of the coating. When the upper limit is exceeded, there is a risk that the water resistance of the coating film is lowered. Moreover, if it is less than the lower limit, the effect of addition may not be sufficiently exhibited. This content is more preferably 0.4 to 2% by weight. By adding this basic dispersant (e) to the intermediate coating composition, the uniform dispersion of the intermediate coating composition and the stability of the coating during storage can be improved.
その他の成分
本発明の中塗り塗料組成物は、上記の成分（ａ）〜成分（ｅ）に加えて、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、エポキシ樹脂等を含んでもよい。これらの樹脂は特に限定されるものではない。これらの樹脂は１種で用いてもよく、２種以上を併用して用いてもよい。
Other Components In addition to the above components (a) to (e), the intermediate coating composition of the present invention may contain an acrylic resin, a polyester resin, an alkyd resin, an epoxy resin and the like. These resins are not particularly limited. These resins may be used alone or in combination of two or more.
本発明の中塗り塗料組成物は、着色顔料、体質顔料などの顔料を含んでもよい。着色顔料として、例えば有機系のアゾキレート系顔料、不溶性アゾ系顔料、縮合アゾ系顔料、ジケトピロロピロール系顔料、ベンズイミダゾロン系顔料、フタロシアニン系顔料、インジゴ顔料、ペリノン系顔料、ペリレン系顔料、ジオキサン系顔料、キナクリドン系顔料、イソインドリノン系顔料、金属錯体顔料等が挙げられ、無機系では黄鉛、黄色酸化鉄、ベンガラ、カーボンブラック、二酸化チタン等を用いることができる。また、体質顔料として、炭酸カルシウム、硫酸バリウム、アルミニウム粉、カオリン等を用いることができる。 The intermediate coating composition of the present invention may contain pigments such as colored pigments and extender pigments. Examples of color pigments include organic azo chelate pigments, insoluble azo pigments, condensed azo pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, Examples thereof include dioxane pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, and inorganic pigments such as yellow lead, yellow iron oxide, bengara, carbon black, and titanium dioxide can be used. In addition, calcium carbonate, barium sulfate, aluminum powder, kaolin and the like can be used as extender pigments.
標準的には、カーボンブラックと二酸化チタンとを主要顔料としたグレー系のものが用いられる。更に、上塗りとの色相を合わせたものや各種の着色顔料を組み合わせたものを用いることもできる。 As a standard, a gray type having carbon black and titanium dioxide as main pigments is used. Furthermore, the thing which combined the hue with top coat and the thing which combined various coloring pigments can also be used.
本発明の中塗り塗料組成物は、一般に用いられる粘性制御剤を含んでもよい。粘性制御剤を含むことによって、上塗り塗膜とのなじみ防止、塗装作業性を確保することができる。粘性制御剤としては、一般にチクソトロピー性を示すものを含有でき、例えば、脂肪酸アマイドの膨潤分散体、アマイド系脂肪酸、長鎖ポリアミノアマイドの燐酸塩等のポリアマイド系のもの、酸化ポリエチレンのコロイド状膨潤分散体等のポリエチレン系のもの、有機酸スメクタイト粘土、モンモリロナイト等の有機ベントナイト系のもの、ケイ酸アルミ、硫酸バリウム等の無機顔料、顔料の形状により粘性が発現する扁平顔料等を粘性制御剤として挙げることができる。 The intermediate coating composition of the present invention may contain a commonly used viscosity controlling agent. By including the viscosity control agent, it is possible to prevent the compatibility with the top coat film and to ensure the painting workability. Viscosity control agents can generally include those exhibiting thixotropy, such as fatty acid amide swelling dispersions, amide fatty acids, polyamides such as long-chain polyaminoamide phosphates, colloidal swelling dispersion of oxidized polyethylene Examples of viscosity control agents include polyethylene-based materials, organic acid smectite clays, organic bentonite-based materials such as montmorillonite, inorganic pigments such as aluminum silicate and barium sulfate, and flat pigments that develop viscosity depending on the shape of the pigment. be able to.
本発明の中塗り塗料組成物は、塗料に通常添加される添加剤、例えば、表面調整剤、酸化防止剤、消泡剤等を含むこともできる。これらの配合量は当業者の公知の範囲である。 The intermediate coating composition of the present invention can also contain additives that are usually added to coatings, such as surface conditioners, antioxidants, antifoaming agents, and the like. These compounding amounts are within the range known to those skilled in the art.
中塗り塗料組成物の調製
本発明の中塗り塗料組成物は、上記塩基性分散剤（ｅ）を、中塗り塗料組成物中のその他の樹脂や有機溶剤を混合させた後に混合分散させる順序で製造されることが好ましい。塗料と上記塩基性分散剤（ｅ）との混合方法は、特に限定されないが、通常の低シェアーでの撹拌、ホモジナイザーなどでの高シェアー撹拌、あるいは、超音波などを使用して行ってもよい。上記分散方法によれば、その他の樹脂や溶剤を加えて加工を施しても、なお優れた貯蔵安定性を保つことができる。
Preparation of intermediate coating composition In the intermediate coating composition of the present invention, the basic dispersant (e) is mixed and dispersed in the order of mixing other resins and organic solvents in the intermediate coating composition. Preferably it is manufactured. The mixing method of the coating material and the basic dispersant (e) is not particularly limited, but may be performed using normal low-shear stirring, high-shear stirring with a homogenizer, or ultrasonic waves. . According to the above dispersion method, excellent storage stability can be maintained even if other resins or solvents are added and processed.
本発明で用いられる中塗り塗料組成物の塗装時の全固形分量は、３０〜８０重量％であり、好ましくは３５〜６５重量％である。この範囲外では塗料安定性が低下する。また上限を越えると、粘性が高すぎて塗膜外観が低下し、下限を下回ると粘性が低すぎてなじみやムラ等の外観不良が発生する。 The total solid content during coating of the intermediate coating composition used in the present invention is 30 to 80% by weight, preferably 35 to 65% by weight. Outside this range, the paint stability is reduced. When the upper limit is exceeded, the viscosity is too high and the appearance of the coating film is lowered. When the viscosity is lower than the lower limit, the viscosity is too low and appearance defects such as familiarity and unevenness occur.
本発明に用いられる塗料組成物の製造方法は、後述するものを含めて、特に限定されず、顔料等の配合物をニーダーまたはロール、ＳＧミル等を用いて混練、分散する等の当業者に周知の全ての方法を用い得る。 The method for producing the coating composition used in the present invention is not particularly limited, including those described later. For those skilled in the art such as kneading and dispersing a compound such as a pigment using a kneader or a roll, an SG mill or the like. All known methods can be used.
ベース塗膜
本発明の塗膜形成方法において用いられるベース塗料組成物は、クリヤー塗料組成物と共に上塗り塗膜を構成するために用いるものである。このベース塗料組成物には、塗膜形成性樹脂、硬化剤、着色顔料、必要に応じて光輝性顔料等が含まれる。
Base coating film The base coating composition used in the coating film forming method of the present invention is used for constituting a top coating film together with a clear coating composition. The base coating composition contains a film-forming resin, a curing agent, a color pigment, and a glitter pigment as necessary.
上記ベース塗料組成物に含有される塗膜形成性樹脂としては、特に限定されるものではなく、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、ウレタン樹脂等を好ましいものとして挙げることができ、１種または２種以上を併用して用いることができる。 The film-forming resin contained in the base coating composition is not particularly limited, and preferred examples include acrylic resins, polyester resins, alkyd resins, epoxy resins, urethane resins, and the like. Two or more species can be used in combination.
上記塗膜形成性樹脂は、硬化剤と組み合わせて用いることができるが、得られた塗膜の諸性能、コストの点からアミノ樹脂および／またはブロックイソシアネート樹脂が好ましいものとして用いられる。 Although the said film-forming resin can be used in combination with a hardening | curing agent, the amino resin and / or block isocyanate resin are used as a preferable thing from the point of the various performance of the obtained coating film, and cost.
上記硬化剤の含有量は、塗膜形成性樹脂の固形分重量に対して２０〜６０重量％とすることが好ましく、更に好ましくは３０〜５０重量％である。含有量が下限を下回ると硬化性が不十分となり、上限を上回ると硬化膜が堅くなりすぎ脆くなる。 The content of the curing agent is preferably 20 to 60% by weight, more preferably 30 to 50% by weight, based on the solid content weight of the film-forming resin. When the content is lower than the lower limit, the curability becomes insufficient, and when the content exceeds the upper limit, the cured film becomes too hard and brittle.
また、上記着色顔料としては、例えば、上述の中塗り塗料組成物についての記載で挙げたもの等を含有することができる。 Moreover, as said coloring pigment, what was mentioned by the description about the above-mentioned intermediate coating composition can be contained, for example.
上記ベース塗料組成物に必要に応じて含まれる光輝性顔料としては、形状は特に限定されず、更に着色されていても良いが、例えば、平均粒径（Ｄ５０）が２〜５０μｍであり、且つ厚さが０．１〜５μｍであるものが好ましい。また、平均粒径が１０〜３５μｍの範囲のものが光輝感に優れ、更に好適に用いられる。 The glittering pigment contained in the base coating composition as needed is not particularly limited in shape, and may be further colored. For example, the average particle diameter (D50) is 2 to 50 μm, and The thing whose thickness is 0.1-5 micrometers is preferable. Those having an average particle diameter in the range of 10 to 35 μm are excellent in glitter and are more preferably used.
上記塗料組成物中の光輝性顔料の顔料濃度（ＰＷＣ）は、一般的に２０．０重量％以下である。上限を越えると塗膜外観が低下する。好ましくは、０．０１〜１８．０重量％であり、より好ましくは、０．１〜１５．０重量％である。なお「ＰＷＣ」とは、塗料組成物の塗料固形分における顔料の濃度（重量％）である。 The pigment concentration (PWC) of the glitter pigment in the coating composition is generally 20.0% by weight or less. When the upper limit is exceeded, the appearance of the coating film deteriorates. Preferably, it is 0.01-18.0 weight%, More preferably, it is 0.1-15.0 weight%. “PWC” is the concentration (% by weight) of the pigment in the solid content of the coating composition.
上記光輝性顔料としては、アルミニウム、銅、亜鉛、鉄、ニッケル、スズ、酸化アルミニウム等の金属または合金等の無着色あるいは着色された金属製光輝剤およびその混合物が挙げられる。更に、干渉マイカ顔料、ホワイトマイカ顔料、グラファイト顔料その他の着色、有色扁平顔料等を併用しても良い。 Examples of the glitter pigment include non-colored or colored metal glitter such as metals or alloys such as aluminum, copper, zinc, iron, nickel, tin, and aluminum oxide, and mixtures thereof. Further, interference mica pigments, white mica pigments, graphite pigments, and other colored or colored flat pigments may be used in combination.
上記光輝性顔料およびその他の全ての顔料を含めた塗料組成物中の全顔料濃度（ＰＷＣ）としては、０．１〜５０重量％であり、好ましくは、０．５〜４０重量％であり、より好ましくは、１．０〜３０重量％である。上限を越えると塗膜外観が低下する恐れがある。 The total pigment concentration (PWC) in the coating composition including the glitter pigment and all other pigments is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, More preferably, it is 1.0 to 30% by weight. If the upper limit is exceeded, the coating film appearance may be deteriorated.
更に、上記ベース塗料組成物には、上述の中塗り塗料組成物同様に、塗装作業性を確保するために、粘性制御剤を添加することが好ましい。粘性制御剤は、ムラおよびたれのない塗膜を良好に形成するために用いられるのであり、一般にチクソトロピー性を示すものを含有できる。このようなものとして、例えば、上述の中塗り塗料組成物についての記載で挙げたものを含有することができる。 Furthermore, it is preferable to add a viscosity control agent to the base coating composition in order to ensure coating workability as in the case of the intermediate coating composition described above. The viscosity controlling agent is used for forming a coating film without unevenness and sagging, and can generally contain a thixotropic agent. As such a thing, what was mentioned by the description about the above-mentioned intermediate coating composition can be contained, for example.
本発明に用いられるベース塗料組成物中には、上記成分の他に塗料に通常添加される添加剤、例えば、表面調整剤、増粘剤、酸化防止剤、紫外線防止剤、消泡剤等を配合してもよい。これらの配合量は当業者の公知の範囲である。 In the base coating composition used in the present invention, in addition to the above-mentioned components, additives usually added to the coating, such as surface conditioners, thickeners, antioxidants, UV inhibitors, antifoaming agents, etc. You may mix | blend. These compounding amounts are within the range known to those skilled in the art.
本発明で用いられるベース塗料組成物の塗装時の全固形分量は、１０〜６０重量％であり、好ましくは１５〜５０重量％である。上限を越えると、粘性が高すぎて塗膜外観が低下し、下限を下回ると粘性が低すぎてなじみやムラ等の外観不良が発生する。 The total solid content at the time of coating of the base coating composition used in the present invention is 10 to 60% by weight, preferably 15 to 50% by weight. If the upper limit is exceeded, the viscosity is too high and the appearance of the coating film is lowered. If the lower limit is not reached, the viscosity is too low and appearance defects such as familiarity and unevenness occur.
クリヤー塗膜
上記クリヤー塗膜の形成にはクリヤー塗料組成物が用いられる。このクリヤー塗料組成物は、特に限定されず、塗膜形成性熱硬化性樹脂および硬化剤等を含有するものを利用できる。このクリヤー塗料組成物の形態としては、溶剤型、水性型および粉体型のものが挙げられる。
Clear coating film A clear coating composition is used to form the clear coating film. The clear coating composition is not particularly limited, and a clear coating composition containing a film-forming thermosetting resin and a curing agent can be used. Examples of the form of the clear coating composition include solvent type, aqueous type and powder type.
上記溶剤型クリヤー塗料組成物の好ましい例としては、透明性あるいは耐酸エッチング性等の点から、アクリル樹脂および／またはポリエステル樹脂とアミノ樹脂との組合わせ、あるいはカルボン酸・エポキシ硬化系を有するアクリル樹脂および／またはポリエステル樹脂等が挙げられる。 Preferred examples of the solvent-based clear coating composition include acrylic resin and / or a combination of a polyester resin and an amino resin, or an acrylic resin having a carboxylic acid / epoxy curing system in terms of transparency or acid etching resistance. And / or a polyester resin.
また、上記水性型クリヤー塗料組成物の例としては、上記溶剤型クリヤー塗料組成物の例として挙げたものに含有される塗膜形成性樹脂を、塩基で中和して水性化した樹脂を含有するものが挙げることができる。この中和は重合の前または後に、ジメチルエタノールアミンおよびトリエチルアミンのような３級アミンを添加することにより行うことができる。 Examples of the water-based clear coating composition include a resin obtained by neutralizing a film-forming resin contained in the solvent-based clear coating composition described above as an example of the solvent-type clear coating composition with a base. To do. This neutralization can be carried out by adding tertiary amines such as dimethylethanolamine and triethylamine before or after polymerization.
一方、粉体型クリヤー塗料組成物としては、熱可塑性および熱硬化性粉体塗料のような通常の粉体塗料を用い得ることができる。良好な物性の塗膜が得られるため、熱硬化性粉体塗料が好ましい。熱硬化性粉体塗料の具体的なものとしては、エポキシ系、アクリル系およびポリエステル系の粉体クリヤー塗料等が挙げられるが、耐候性が良好なアクリル系粉体クリヤー塗料が特に好ましい。 On the other hand, as the powder type clear coating composition, ordinary powder coatings such as thermoplastic and thermosetting powder coatings can be used. A thermosetting powder coating is preferred because a coating film having good physical properties can be obtained. Specific examples of thermosetting powder coatings include epoxy, acrylic and polyester powder clear coatings, and acrylic powder clear coatings having good weather resistance are particularly preferred.
本発明に用いる粉体型クリヤー塗料として、硬化時の揮散物が無く、良好な外観が得られ、そして黄変が少ないことから、エポキシ含有アクリル樹脂／多価カルボン酸の系の粉体塗料が特に好ましい。 As the powder type clear paint used in the present invention, there is no volatile matter at the time of curing, a good appearance is obtained, and since yellowing is small, an epoxy-containing acrylic resin / polycarboxylic acid type powder paint is used. Particularly preferred.
更に、上記クリヤー塗料組成物には、上述の中塗り塗料組成物同様に、塗装作業性を確保するために、粘性制御剤を添加されていることが好ましい。粘性制御剤は、一般にチクソトロピー性を示すものを含有できる。このようなものとして、例えば、上述の中塗り塗料組成物についての記載で挙げたものを含有することができる。また必要により、硬化触媒、表面調整剤等を含むことができる。 Furthermore, it is preferable that a viscosity control agent is added to the clear coating composition in order to ensure the coating workability as in the case of the intermediate coating composition described above. The viscosity control agent can contain what generally shows thixotropy. As such a thing, what was mentioned by the description about the above-mentioned intermediate coating composition can be contained, for example. Moreover, a curing catalyst, a surface conditioner, etc. can be included if necessary.
基材
本発明の塗膜形成方法は、種々の基材、例えば金属、プラスチック、発泡体等、特に金属表面、および鋳造物に有利に用い得るが、カチオン電着塗装可能な金属製品に対し、特に好適に使用できる。
A method of forming a coating film base present invention, various substrates, such as metals, plastics, foam and the like, but may advantageously be used in particular metal surfaces, and cast, with respect to cation electrodeposition coating capable metal products, It can be particularly preferably used.
上記金属製品としては、例えば、鉄、銅、アルミニウム、スズ、亜鉛等およびこれらの金属を含む合金が挙げられる。具体的には、乗用車、トラック、オートバイ、バス等の自動車車体および部品が挙げられる。これらの金属は予めリン酸塩、クロム酸塩等で化成処理されたものが特に好ましい。 Examples of the metal products include iron, copper, aluminum, tin, zinc and the like and alloys containing these metals. Specific examples include automobile bodies and parts such as passenger cars, trucks, motorcycles, and buses. These metals are particularly preferably those subjected to chemical conversion treatment with phosphate, chromate or the like in advance.
また、本発明に用いられる基材には、化成処理された鋼板上に電着塗膜が形成されていても良い。電着塗膜を形成する電着塗料組成物としては、カチオン型およびアニオン型を使用できるが、カチオン型電着塗料組成物が防食性において優れた積層塗膜を与えるため好ましい。 Moreover, the electrodeposition coating film may be formed in the base material used for this invention on the steel plate by which chemical conversion treatment was carried out. As an electrodeposition coating composition for forming an electrodeposition coating film, a cation type and an anion type can be used, but a cationic type electrodeposition coating composition is preferable because it provides a laminated coating film excellent in corrosion resistance.
塗膜形成方法
本発明の塗膜形成方法では、電着塗膜が形成された基材の上に、中塗り塗料組成物、ベース塗料組成物およびクリヤー塗料組成物を、順次塗装する工程、塗装された三層を一度に焼付け硬化させる３コート１ベーク法で、上記中塗り塗料組成物を用いて塗膜形成することができる。
Coating film forming method In the coating film forming method of the present invention, an intermediate coating composition, a base coating composition, and a clear coating composition are sequentially applied onto a substrate on which an electrodeposition coating film is formed, A coating film can be formed using the above-mentioned intermediate coating composition by a three-coat one-bake method in which the three layers thus obtained are baked and cured at a time.
本発明で上記中塗り塗料組成物を、例えば自動車車体に塗装する場合は、外観を高めるために、エアー静電スプレー塗装による多ステージ塗装、好ましくは２ステージで塗装するか、或いは、エアー静電スプレー塗装と、通称「μμ（マイクロマイクロ）ベル」、「μ（マイクロ）ベル」あるいは「メタベル」等と言われる回転霧化式の静電塗装機とを組み合わせた塗装方法等により塗膜を形成することができる。 In the present invention, when the intermediate coating composition is applied to an automobile body, for example, in order to enhance the appearance, it is applied by multi-stage coating by air electrostatic spray coating, preferably two stages, or air electrostatic Forming a coating film by spray coating and a coating method that combines a so-called “μμ (micro micro) bell”, “μ (micro) bell” or “metabell” rotary atomizing electrostatic coating machine can do.
本発明における、中塗り塗料組成物による乾燥塗膜の膜厚は所望の用途により変化するが、多くの場合１０〜６０μｍが有用である。上限を越えると、鮮映性が低下したり、塗装時にムラあるいは流れ等の不具合が起こることがあり、下限を下回ると、下地が隠蔽できず膜切れが発生する。 In the present invention, the film thickness of the dried coating film by the intermediate coating composition varies depending on the desired application, but in many cases, 10 to 60 μm is useful. If the upper limit is exceeded, sharpness may deteriorate, or defects such as unevenness or flow may occur during coating. If the lower limit is exceeded, the substrate cannot be concealed and film breakage occurs.
本発明の塗膜形成方法では更に、未硬化の中塗り塗膜の上に、ベース塗料組成物およびクリヤー塗料組成物をウェットオンウェットで塗布し、未硬化のベース塗膜およびクリヤー塗膜を形成する。 In the coating film forming method of the present invention, the base coating composition and the clear coating composition are further applied on the uncured intermediate coating film by wet-on-wetting to form an uncured base coating film and a clear coating film. To do.
本発明の方法におけるベース塗膜を形成する為に用いるベース塗料組成物は、上記中塗り塗料組成物と同様に、エアー静電スプレー塗装あるいはメタベル、μμベル、μベル等の回転霧化式の静電塗装機により塗装することができる。ベース塗膜の乾燥膜厚は５〜３５μｍに設定することができ、好ましくは７〜２５μｍである。ベース塗膜の膜厚が上限を上回ると鮮映性が低下したり、塗膜にムラまたは流れが生じることがあり、また下限を下回ると下地隠蔽性が不充分となり、膜切れ（塗膜が不連続な状態）が生じることがあるため、いずれも好ましくない。 The base coating composition used for forming the base coating film in the method of the present invention is, like the above intermediate coating composition, air electrostatic spray coating or rotary atomization type such as Metabell, μμ Bell, μ Bell, etc. Can be painted with an electrostatic coating machine. The dry film thickness of a base coating film can be set to 5-35 micrometers, Preferably it is 7-25 micrometers. If the film thickness of the base coating film exceeds the upper limit, the sharpness may decrease or the coating film may become uneven or flow. None of these is preferable because a discontinuous state) may occur.
本発明の塗膜形成方法において、上記ベース塗膜を形成した後に塗装されるクリヤー塗膜は、上記ベース塗膜に起因する凹凸、光輝性顔料が含まれる場合に起こるチカチカ等を平滑にし、保護するために形成される。塗装方法として具体的には、先に述べたμμベル、μベル等の回転霧化式の静電塗装機により塗膜形成することが好ましい。 In the method for forming a coating film according to the present invention, the clear coating film that is applied after the base coating film is formed smoothes and protects the unevenness caused by the base coating film and the flickering that occurs when a bright pigment is included. Formed to do. Specifically, as a coating method, it is preferable to form a coating film by the above-described rotary atomizing electrostatic coater such as μμ bell or μbell.
上記クリヤー塗料組成物により形成されるクリヤー塗膜の乾燥膜厚は、一般に１０〜８０μｍ程度が好ましく、より好ましくは２０〜６０μｍ程度である。上限を越えると、塗装時にワキあるいはタレ等の不具合が起こることもあり、下限を下回ると、下地の凹凸が隠蔽しきれず、塗膜外観が劣る恐れがある。 The dry film thickness of the clear coating film formed from the clear coating composition is generally preferably about 10 to 80 μm, more preferably about 20 to 60 μm. If the upper limit is exceeded, defects such as cracks or sagging may occur during coating, and if the lower limit is exceeded, the underlying irregularities cannot be concealed and the coating film appearance may be inferior.
上述のようにして得られた積層された未硬化の塗膜は、同時に加熱硬化される。この塗膜形成方法は一般に、３コート１ベーク法といわれる。この方法は、焼き付け乾燥炉を省略することができ、経済性および環境面からも好ましい。 The laminated uncured coating film obtained as described above is heated and cured simultaneously. This coating film forming method is generally referred to as a three-coat one-bake method. This method can omit the baking and drying furnace, and is preferable from the viewpoint of economy and environment.
上記積層塗膜を硬化させる硬化温度を１００〜１８０℃、好ましくは１３０〜１６０℃に設定することで高い架橋度の硬化塗膜が得られる。上限を越えると、塗膜が固く脆くなり、下限未満では硬化が充分でない。硬化時間は硬化温度により変化するが、１３０℃〜１６０℃で１０〜３０分が適当である。 A cured coating film having a high degree of crosslinking can be obtained by setting the curing temperature for curing the laminated coating film to 100 to 180 ° C, preferably 130 to 160 ° C. If the upper limit is exceeded, the coating film becomes hard and brittle, and if it is less than the lower limit, curing is not sufficient. The curing time varies depending on the curing temperature, but 10 to 30 minutes is appropriate at 130 to 160 ° C.
本発明で形成される積層塗膜の膜厚は、多くの場合３０〜３００μｍであり、好ましくは５０〜２５０μｍである。上限を越えると、冷熱サイクル等の膜物性が低下する恐れがある。また下限を下回ると膜自体の強度が低下する恐れがある。 The film thickness of the laminated coating film formed in the present invention is often 30 to 300 μm, and preferably 50 to 250 μm. If the upper limit is exceeded, film properties such as cooling and cooling cycles may be deteriorated. If the lower limit is not reached, the strength of the film itself may be reduced.
以下、具体的な実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例により限定されるものではない。尚、以下に於いて「部」とあるのは「重量部」を意味する。 EXAMPLES Hereinafter, although a specific Example is given and this invention is demonstrated in detail, this invention is not limited by a following example. In the following description, “part” means “part by weight”.
製造例１
ウレタン変性ポリエステル樹脂の製造
窒素導入管、撹拌機、温度調節機、滴下ロートおよびデカンターを備えた冷却管を取り付けた２Ｌの反応容器にイソフタル酸４４０部、ヘキサヒドロフタル酸２０部、アゼライン酸４０部、トリメチロールプロパン３００部およびネオペンチルグリコール２００部とを仕込み、加熱により原料が溶解し撹拌可能となったところで、ジブチル錫オキサイド０．２部を投入し、撹拌を開始し、反応層温度を１８０から２２０℃まで３時間かけて徐々に昇温した。生成する縮合水は系外へ留去した。２２０℃に達したところで、１時間保温し、反応層内にキシレン２０部を徐々に添加し、溶剤存在化で縮合反応を進行させた。樹脂酸価が１０ｍｇＫＯＨ／ｇに達したところで、１００℃に冷却し、ヘキサメチレンジイソシアネート１００部を３０分間かけて徐々に添加した。更に、１時間保持後、キシレン２００部および酢酸ブチル２００部を加え、固形分７０％、数平均分子量２０００、酸価８ｍｇＫＯＨ／ｇ、水酸基価１２０、樹脂Ｔｇ６０℃のウレタン変性ポリエステル樹脂を得た。
Production Example 1
Manufacture of urethane-modified polyester resin 440 parts of isophthalic acid, 20 parts of hexahydrophthalic acid, 40 parts of azelaic acid in a 2 L reaction vessel equipped with a nitrogen introducing tube, a stirrer, a temperature controller, a cooling tube equipped with a dropping funnel and a decanter Then, 300 parts of trimethylolpropane and 200 parts of neopentylglycol were charged, and when the raw material was dissolved and stirred by heating, 0.2 part of dibutyltin oxide was added, stirring was started, and the reaction layer temperature was set at 180 ° C. The temperature was gradually raised to 220 ° C. over 3 hours. The resulting condensed water was distilled out of the system. When the temperature reached 220 ° C., the temperature was kept for 1 hour, 20 parts of xylene was gradually added into the reaction layer, and the condensation reaction proceeded in the presence of a solvent. When the resin acid value reached 10 mgKOH / g, it was cooled to 100 ° C., and 100 parts of hexamethylene diisocyanate was gradually added over 30 minutes. Furthermore, after maintaining for 1 hour, 200 parts of xylene and 200 parts of butyl acetate were added to obtain a urethane-modified polyester resin having a solid content of 70%, a number average molecular weight of 2000, an acid value of 8 mgKOH / g, a hydroxyl value of 120, and a resin Tg of 60 ° C.
製造例２
非水ディスパージョン（１）の製造
（ａ）分散安定樹脂の製造
攪拌機、温度制御装置、還流冷却器を備えた容器に酢酸ブチル９０部を仕込んだ。次に下記組成の溶液メタクリル酸メチル３８．９部、ステアリルメタクリレート３８．８部、２−ヒドロキシエチルアクリレート２２．３部およびアゾビスイソブチロニトリル５．０部の内２０部を加え、攪拌しながら加熱し、温度を上昇させた。１１０℃で上記混合溶液の残り８５部を３時間で滴下し、次いでアゾビスイソブチロニトリル０．５部と酢酸ブチル１０部からなる溶液を３０分間で滴下した。反応溶液をさらに２時間攪拌還流させて樹脂への変化率を上昇させた後、反応を終了させ、固形分５０％、数平均分子量５６００のアクリル樹脂を得た。
Production Example 2
Production of Non-Aqueous Dispersion (1) (a) Production of Dispersion Stabilizing Resin 90 parts of butyl acetate was charged into a vessel equipped with a stirrer, a temperature controller and a reflux condenser. Next, 20 parts of 38.9 parts methyl methacrylate, 38.8 parts stearyl methacrylate, 22.3 parts 2-hydroxyethyl acrylate and 5.0 parts azobisisobutyronitrile having the following composition were added and stirred. While heating, the temperature was raised. The remaining 85 parts of the above mixed solution was added dropwise at 110 ° C. over 3 hours, and then a solution consisting of 0.5 parts of azobisisobutyronitrile and 10 parts of butyl acetate was added dropwise over 30 minutes. The reaction solution was further stirred and refluxed for 2 hours to increase the rate of conversion to resin, and the reaction was terminated to obtain an acrylic resin having a solid content of 50% and a number average molecular weight of 5600.
（ｂ）非水ディスパージョンの製造
攪拌機、冷却器、温度制御装置を備えた容器に酢酸ブチル３５部、上記の（ａ）分散安定樹脂の製造で得たアクリル樹脂６０部を仕込んだ。次に、スチレン７．０部、エチルアクリレート８．５部、メチルメタクリレート１２．０部、メタクリル酸１．８部、２−ヒドロキシエチルメタクリレート４０．７部、およびアゾビスイソブチロニトリル １．４部からなるモノマー混合溶液を、１００℃で３時間かけて滴下し、更に、アゾビスイソブチロニトリル０．１部と酢酸ブチル１部からなる溶液を３０分間で滴下した。反応溶液をさらに１時間攪拌を続けたところ、固形分６６％、粒子径０．１８μｍのエマルジョンを得た。このエマルジョンを酢酸ブチルで希釈し、非水ディスパージョン（１）含量４０重量％の酢酸ブチル分散体を得た。
(B) Production of non-aqueous dispersion A container equipped with a stirrer, a cooler, and a temperature controller was charged with 35 parts of butyl acetate and 60 parts of acrylic resin obtained in the production of (a) the dispersion-stable resin. Next, 7.0 parts of styrene, 8.5 parts of ethyl acrylate, 12.0 parts of methyl methacrylate, 1.8 parts of methacrylic acid, 40.7 parts of 2-hydroxyethyl methacrylate, and azobisisobutyronitrile 1.4 A monomer mixed solution consisting of 1 part was added dropwise at 100 ° C. over 3 hours, and a solution consisting of 0.1 part of azobisisobutyronitrile and 1 part of butyl acetate was added dropwise over 30 minutes. When the reaction solution was further stirred for 1 hour, an emulsion having a solid content of 66% and a particle size of 0.18 μm was obtained. This emulsion was diluted with butyl acetate to obtain a butyl acetate dispersion having a non-aqueous dispersion (1) content of 40% by weight.
製造例３
非水ディスパージョン（２）の製造
攪拌機、冷却器、温度制御装置を備えた容器に酢酸ブチル３５部、上記の非架橋重合体粒子の製造例（１）の（ａ）分散安定樹脂の製造で得たアクリル樹脂１００部を仕込んだ。次に、メタクリル酸１．３部、メタクリル酸メチル１８．４部、エチルアクリレート１８．２部、２−ヒドロキシエチルメタクリレート１２．２部およびアゾビスイソブチロニトリル１．４部からなるモノマー混合溶液を、１００℃で３時間かけて滴下し、更に、アゾビスイソブチロニトリル０．１部と酢酸ブチル１部からなる溶液を３０分間で滴下した。反応溶液をさらに１時間攪拌を続けたところ、固形分５４％、粒子径０．１４μｍのエマルションを得た。このエマルジョンを酢酸ブチルで希釈し、非水ディスパージョン（２）含量４０重量％の酢酸ブチル分散体を得た。
Production Example 3
Production of non-aqueous dispersion (2) 35 parts of butyl acetate in a vessel equipped with a stirrer, cooler and temperature control device, (a) Production of dispersion-stable resin in production example (1) of the above non-crosslinked polymer particles 100 parts of the obtained acrylic resin was charged. Next, a monomer mixed solution comprising 1.3 parts of methacrylic acid, 18.4 parts of methyl methacrylate, 18.2 parts of ethyl acrylate, 12.2 parts of 2-hydroxyethyl methacrylate and 1.4 parts of azobisisobutyronitrile. Was added dropwise at 100 ° C. over 3 hours, and a solution consisting of 0.1 part of azobisisobutyronitrile and 1 part of butyl acetate was added dropwise over 30 minutes. When the reaction solution was further stirred for 1 hour, an emulsion having a solid content of 54% and a particle size of 0.14 μm was obtained. This emulsion was diluted with butyl acetate to obtain a butyl acetate dispersion having a non-aqueous dispersion (2) content of 40% by weight.
実施例１
中塗り塗料組成物
１Ｌのベッセルに、先の製造例で得られたウレタン変性ポリエステル樹脂ワニス１０７部、ＣＲ−９７（石原産業社製酸化チタン）２８０部、ＭＡ−１００（三菱化学社製カーボンブラック顔料）１３部、ＬＭＳ−１００（富士タルク社製鱗片状タルク）７部、酢酸ブチル４７部およびキシレン４７部を仕込み、仕込み重量と同量のＧＢ５０３Ｍ（粒径１．６ｍｍガラスビーズ）を投入し、卓上ＳＧミルを用いて室温で３時間分散し、灰色の顔料ペーストとした。グラインドゲージによる分散終了時の粒度は５μｍ以下であった。ガラスビーズを濾過して顔料ペーストを得た。
Example 1
A vessel of the intermediate coating composition 1L, urethane-modified polyester resin varnish 107 parts obtained in the preceding production example, CR-97 (Ishihara Sangyo Kaisha Ltd. Titanium oxide) 280 parts, MA-100 (manufactured by Mitsubishi Chemical Corporation Carbon black Pigment) 13 parts, LMS-100 (Fuji talc scale talc) 7 parts, butyl acetate 47 parts and xylene 47 parts were charged, and GB503M (particle diameter 1.6 mm glass beads) of the same amount as the charged weight was charged. The mixture was dispersed for 3 hours at room temperature using a tabletop SG mill to obtain a gray pigment paste. The particle size at the end of dispersion by a grind gauge was 5 μm or less. The glass beads were filtered to obtain a pigment paste.
上記顔料ペースト１００部に、上記製造例１のウレタン変性ポリエステル樹脂１３０部、製造例２の非水ディスパージョン（１）５３部、ユーバン１２８（三井化学社製メラミン樹脂、固形分６０％）７１部、デュラネートＭＦ−Ｋ６０Ｘ（旭化成社製活性メチレン型ブロックイソシアネート、固形分６０％）７１部を混合して中塗り塗料組成物を調製した。 To 100 parts of the pigment paste, 130 parts of the urethane-modified polyester resin of Production Example 1, 53 parts of the non-aqueous dispersion (1) of Production Example 2, and 71 parts of Uban 128 (Mitsui Chemicals melamine resin, solid content 60%) An intermediate coating composition was prepared by mixing 71 parts of Duranate MF-K60X (active methylene type blocked isocyanate manufactured by Asahi Kasei Corporation, solid content 60%).
更に、エトキシエチルプロピオネート／Ｓ−１００（エクソン社製芳香族炭化水素溶剤）＝１／１の混合溶剤で、Ｎｏ．４フォードカップを用いて１９秒／２０℃に希釈調整した。塗布時の不揮発分は４９％であった。 Further, a mixed solvent of ethoxyethyl propionate / S-100 (Aromatic hydrocarbon solvent manufactured by Exxon) = 1/1. The dilution was adjusted to 19 seconds / 20 ° C. using a 4 Ford cup. The nonvolatile content at the time of application was 49%.
また更に、上記中塗り塗料組成物の固形分に対して、Ｄｉｓｐｅｒｂｙｋ １８２（ビックケミー社製３級アミン含有塩基性分散剤、固形分４３％）が０．３重量％となるように混合し、ディスパーで分散した。 Further, Dispersbyk 182 (Bic Chemie's tertiary amine-containing basic dispersant, 43% solid content) is mixed with the solid content of the intermediate coating composition so as to be 0.3% by weight. Dispersed.
ベース塗料組成物
日本ペイント社製アクリルメラミン系メタリックベース塗料「オルガＴＯ Ｈ６００ １８Ｊ グリーンメタリック」を用い、エトキシエチルプロピオネート／Ｓ−１００（エクソン社製芳香族炭化水素溶剤）／トルエン＝１／１／２の混合溶剤で、Ｎｏ．３フォードカップを用いて１７秒／２０℃に希釈調整した。
Base paint composition An acrylic melamine-based metallic base paint “Orga TO H600 18J Green Metallic” manufactured by Nippon Paint Co., Ltd., ethoxyethyl propionate / S-100 (exxon aromatic hydrocarbon solvent) / toluene = 1/1 No./2 mixed solvent. The dilution was adjusted to 17 seconds / 20 ° C. using a 3 Ford cup.
クリヤー塗料組成物
日本ペイント社製酸エポキシ硬化系クリヤー塗料「マック Ｏ−１６００ クリヤー」を用い、エトキシエチルプロピオネート／Ｓ−１００（エクソン社製芳香族炭化水素溶剤）＝１／１の混合溶剤で、Ｎｏ．４フォードカップを用いて２６秒／２０℃に希釈調整した。
Clear paint composition A mixed solvent of ethoxyethyl propionate / S-100 (Aromatic hydrocarbon solvent manufactured by Exxon) = 1/1 using acid epoxy curable clear paint “Mac O-1600 Clear” manufactured by Nippon Paint Co., Ltd. No. The dilution was adjusted to 26 seconds / 20 ° C. using a 4 Ford cup.
積層塗膜の形成
厚さ０．８ｍｍ、縦３０ｃｍ、横１０ｃｍのリン酸亜鉛処理したＳＰＣ鋼板に、カチオン電着塗料「パワートップＶ−２０」（日本ペイント社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板を用意した。次に、移動体に貼着し、移動させながら先の中塗り塗料組成物を乾燥膜厚が２０μｍとなるように「マイクロベル」（回転霧化型静電塗装機）で塗装し、塗布後に１０分間のインターバルをとり、セッティングを行った。
On the SPC steel plate treated with zinc phosphate of 0.8mm thickness, 30cm length and 10cm width, the thickness of the laminated coating film is applied to the cationic electrodeposition paint "Power Top V-20" (manufactured by Nippon Paint Co., Ltd.) with a dry film thickness of 20μm. A coated plate was prepared by electrodeposition coating so as to be baked at 160 ° C. for 30 minutes. Next, it is attached to a moving body, and the intermediate coating composition is applied with a “Microbell” (rotary atomization type electrostatic coating machine) so that the dry film thickness is 20 μm while being moved. A setting was made after an interval of 10 minutes.
次いで、先のベース塗料組成物を、乾燥膜厚１５μｍとなるように「マイクロベル」と「メタベル」で２ステージ塗装した。２回の塗布の間に、２．５分間のインターバルを行った。２回目の塗布後、８分間セッティングを行った。次に、先のクリヤー塗料組成物を、乾燥膜厚３５μｍとなるように「マイクロベル」により、１ステージ塗装し、７分間セッティングした。ついで、得られた塗装板を１４０℃の乾燥機で３０分間焼き付けした。 Subsequently, the above base coating composition was applied in two stages with “Microbell” and “Metabell” so as to have a dry film thickness of 15 μm. There was a 2.5 minute interval between the two applications. After the second application, setting was performed for 8 minutes. Next, the above clear coating composition was applied for one stage by “Microbell” so as to have a dry film thickness of 35 μm and set for 7 minutes. Next, the obtained coated plate was baked for 30 minutes with a dryer at 140 ° C.
得られた積層塗膜は、塗膜の仕上がり外観、特に艶感について優れ、従来の３コート２ベークで形成した塗膜と遜色ないすばらしい外観であった。 The resulting laminated coating film was excellent in the finished appearance of the coating film, in particular, glossiness, and had a wonderful appearance comparable to a coating film formed by conventional 3-coat 2-bake.
以下の評価方法に従って、得られた中塗り塗料組成物の評価を実施した。
＜貯蔵安定性＞
上記方法と同様の手順で、中塗り塗料組成物を４Ｌ丸缶に希釈した状態で４Ｋｇ製造した。ステンレス製の３２０メッシュの金網で中塗り塗料組成物を濾過し、試験用塗料を調整した。その後、５０℃で１０日間静置し、その塗料を、再びステンレス製の３２０メッシュの金網で塗料を濾過し、濾過残渣を調べた。金網上に残った濾過残渣を１４０℃で２０分間乾燥し、得られたその重量およびその内容物を目視で観察し、下記の判断基準で評価した。
The obtained intermediate coating composition was evaluated according to the following evaluation method.
<Storage stability>
In the same procedure as the above method, 4 kg was produced in a state where the intermediate coating composition was diluted in a 4 L round can. The intermediate coating composition was filtered with a stainless steel 320 mesh wire mesh to prepare a test coating. Then, it was left to stand at 50 ° C. for 10 days, and the paint was filtered again with a 320-mesh metal mesh made of stainless steel, and the filtration residue was examined. The filtration residue remaining on the wire mesh was dried at 140 ° C. for 20 minutes, and the weight and contents obtained were visually observed and evaluated according to the following criteria.
尚、参考までに実施例１の非水ディスパージョン（１）を配合しない中塗り塗料組成物を製造し、同様に静置したところ、濾過した場合の濾過残渣は、１．２７ｍｇであった。残渣の内容物は、問題とはならない毛ゴミのみであったことから、樹脂粒子に起因する塗料系内の不均一化が、貯蔵安定性の原因であるとわかった。 For reference, an intermediate coating composition containing no non-aqueous dispersion (1) of Example 1 was prepared and allowed to stand in the same manner. As a result, the filtration residue was 1.27 mg. Since the content of the residue was only hair dust that was not a problem, it was found that non-uniformization in the coating system caused by the resin particles was the cause of storage stability.
判断基準
顔料ブツ；顔料と樹脂とが混じったグレー色の塗料ブツ。
毛ゴミ；塗料製造時あるいは静置時に混入したゴミと考えられるもの。濾過により採取されても問題無しと判断できるものである。
Judgment Criteria Pigment: Gray paint with a mixture of pigment and resin.
Hair dust: What is considered to be dust mixed during paint production or standing. Even if collected by filtration, it can be determined that there is no problem.
＜耐温水試験＞
得られた塗膜を硬化させた後、４０℃の温水に１０日間浸せきした。引き上げた後、塗板を水洗し、更に水分をふき取った後に、目視により塗膜の表面状態を観察し、次に、刃先が素地に達する程度の深さで、カーターナイフを用いて、２ｍｍ間隔で縦横１１本の平行な線を引き、１００個の升目を形成した。その上にニチバン社製セロファンテープを密着させ、垂直上方に引き剥がした後の、残存した塗膜状態を観察して、付着性の評価とし、以下の判断基準で評価した。
<Hot water resistance test>
After hardening the obtained coating film, it was immersed in 40 degreeC warm water for 10 days. After lifting, the coated plate is washed with water, and after further wiping off water, the surface condition of the coating film is visually observed, and then at a depth of 2 mm with a carter knife at such a depth that the cutting edge reaches the substrate. Eleven parallel lines were drawn vertically and horizontally to form 100 squares. A cellophane tape manufactured by Nichiban Co., Ltd. was in close contact therewith, and the state of the remaining coating film was observed after peeling off vertically upward to evaluate adhesion, and evaluated according to the following criteria.
表面状態
○；変化無し。
△；塗膜が若干膨潤し、わずかに変色（白化）している。
×；塗膜が膨潤し、かなり変色（白化）している。
Surface condition ○: No change.
Δ: The coating film is slightly swollen and slightly discolored (whitened).
X: The coating film is swollen and considerably discolored (whitened).
付着性
○；全く剥離無し。
△；塗膜が升目に沿って、わずかに剥離している。
×；塗膜上に作成した升目が一部剥離している。
Adhesiveness ○: No peeling at all.
(Triangle | delta); The coating film has peeled slightly along the grid.
X: A part of the mesh created on the coating film is peeled off.
実施例２
実施例１で用いた塩基性分散剤の添加量を中塗り塗料組成物の固形分に対して０．５重量％に変更したこと以外は実施例１と同様に中塗り塗料組成物を調製し、実施例１と同様に評価した。
Example 2
An intermediate coating composition was prepared in the same manner as in Example 1 except that the amount of the basic dispersant used in Example 1 was changed to 0.5% by weight based on the solid content of the intermediate coating composition. Evaluation was conducted in the same manner as in Example 1.
実施例３
実施例１で用いた非水ディスパージョン（１）５３部を非水ディスパージョン（２）に５３部に替え、更に塩基性分散剤を、Ｄｉｓｐｅｒｂｙｋ １６１（ビックケミー社製３級アミン含有塩基性分散剤、固形分５２％）０．５重量％に替えたこと以外は実施例１と同様に中塗り塗料組成物を調製し、実施例１と同様に評価した。
Example 3
53 parts of the non-aqueous dispersion (1) used in Example 1 was replaced with 53 parts of the non-aqueous dispersion (2), and the basic dispersant was Disperbyk 161 (a tertiary amine-containing basic dispersant manufactured by Big Chemie). The solid coating composition was prepared in the same manner as in Example 1 except that the solid content was changed to 0.5% by weight, and evaluated in the same manner as in Example 1.
実施例４
実施例１で用いた塩基性分散剤を、ソルスパース３２５５０（アビシア社製アミド含有塩基性分散剤、固形分５０％）０．５重量％に替えたこと以外は実施例１と同様に中塗り塗料組成物を調製し、実施例１と同様に評価した。
Example 4
Intermediate coating material as in Example 1, except that the basic dispersant used in Example 1 was changed to 0.5% by weight of Solsperse 32550 (Avidia-made basic dispersant, solid content 50%). Compositions were prepared and evaluated as in Example 1.
実施例５
実施例１で用いた塩基性分散剤を１．０重量％になるように加えたこと以外は実施例１と同様に中塗り塗料組成物を調製し、実施例１と同様に評価した。
Example 5
An intermediate coating composition was prepared in the same manner as in Example 1 except that the basic dispersant used in Example 1 was added to 1.0% by weight, and evaluated in the same manner as in Example 1.
比較例１〜３
先の実施例１で用いた塩基性分散剤を表１で示した配合量になるように添加するか、または添加しないこと以外は、実施例１と同様に中塗り塗料組成物を調製し、実施例１と同様に評価した。
Comparative Examples 1-3
An intermediate coating composition was prepared in the same manner as in Example 1 except that the basic dispersant used in Example 1 was added so as to have the blending amount shown in Table 1 or not added, Evaluation was performed in the same manner as in Example 1.
以上の評価結果を表１に示す。 The above evaluation results are shown in Table 1.
上記実施例で得られた中塗り塗料組成物は、１０日間貯蔵した後においても、濾過残渣として、顔料と樹脂とが混じったようなグレー色の塗料ブツが発生することなく、塗料製造時あるいは静置時に混入したゴミと考えられる毛ゴミのみしか採取されなかった。 The intermediate coating composition obtained in the above examples was not produced during the production of the paint without the occurrence of a gray paint smear in which the pigment and the resin were mixed as a filtration residue even after storage for 10 days. Only hair debris, which was thought to be debris mixed during standing, was collected.
しかし、上記塩基性分散剤の添加量が多い、比較例２の中塗り塗料組成物は、系内に塩基性基が多く存在しすぎるためか、塗膜にした場合に白化する傾向が出たり、付着性が低下する場合があり、耐水性に関する不具合が発生することがわかった。 However, the intermediate coating composition of Comparative Example 2 having a large amount of the basic dispersant added tends to whiten when it is formed into a coating film because there are too many basic groups in the system. It has been found that the adhesion may be lowered, and a problem with water resistance occurs.
また、参考例として非水ディスパージョンを配合しない中塗り塗料組成物についての貯蔵試験も行ったところ、上記の通り貯蔵安定性に優れるものであった。この結果から、貯蔵時に樹脂粒子が起因する塗料系内の不均一化が、中塗り塗料組成物の貯蔵安定性を低くする原因であると推測できる。 In addition, as a reference example, a storage test was conducted on an intermediate coating composition containing no non-aqueous dispersion. As a result, the storage stability was excellent as described above. From this result, it can be inferred that the non-uniformity in the coating system caused by the resin particles during storage is the cause of lowering the storage stability of the intermediate coating composition.
なお、本発明の中塗り塗料組成物を用いて３コート１ベーク法により形成された積層塗膜は、いずれも優れた外観を有するものであった。
In addition, all the laminated coating films formed by the 3-coat 1-bake method using the intermediate coating composition of this invention had the outstanding external appearance.
Claims (3)
メラミン樹脂（ｂ）１０〜３０重量％、
ブロックイソシアネート化合物（ｃ）１５〜３０重量％、
コアシェル構造を有する非水ディスパージョン樹脂（ｄ）４〜１５重量％
（（ａ）乃至（ｄ）の量は塗料樹脂固形分重量を基準にする。）、および、
ポリアクリレート、ポリウレタン、ポリエステルおよびこれらの変性物からなる群から選択される１種以上を主鎖とする高分子である、塩基性分散剤（ｅ）を、塗料固形分重量に対して０．２〜３重量％、
を含有する、中塗り塗料組成物。 Urethane-modified polyester resin (a) 40 to 56% by weight,
Melamine resin (b) 10 to 30% by weight,
Blocked isocyanate compound (c) 15 to 30% by weight,
Non-aqueous dispersion resin (d) having a core-shell structure 4 to 15% by weight
(The amount of (a) to (d) is based on the weight of the solid content of the paint resin), and
Polyacrylates, polyurethanes, one or more selected from the group consisting of polyester and modifications of these is a polymer whose main chain, a basic dispersant (e), with respect to solid content weight 0.2 ~ 3% by weight,
An intermediate coating composition comprising:
請求項１記載の中塗り塗料組成物。 The basic dispersant (e) has at least one basic group selected from the group consisting of a tertiary amino group, a quaternary ammonium group, and a heterocyclic group having a basic nitrogen atom.
The intermediate coating composition according to claim 1 .
該中塗り塗料組成物が請求項１または２記載の中塗り塗料組成物である、積層塗膜の形成方法。 A step of sequentially applying an intermediate coating composition, a base coating composition and a clear coating composition on a substrate on which an electrodeposition coating is formed, and a step of baking and curing the three layers applied at once; A method of forming a coating film comprising:
A method for forming a laminated coating film, wherein the intermediate coating composition is the intermediate coating composition according to claim 1 or 2 .
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