JP4556100B2 - Metallic paint and metallic coating film - Google Patents
Metallic paint and metallic coating film Download PDFInfo
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- JP4556100B2 JP4556100B2 JP2003357235A JP2003357235A JP4556100B2 JP 4556100 B2 JP4556100 B2 JP 4556100B2 JP 2003357235 A JP2003357235 A JP 2003357235A JP 2003357235 A JP2003357235 A JP 2003357235A JP 4556100 B2 JP4556100 B2 JP 4556100B2
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- 238000000576 coating method Methods 0.000 title claims description 110
- 239000011248 coating agent Substances 0.000 title claims description 107
- 239000003973 paint Substances 0.000 title claims description 76
- 239000000463 material Substances 0.000 claims description 58
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 14
- 239000004640 Melamine resin Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010422 painting Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DHQIYHHEPUYAAX-UHFFFAOYSA-N n-(4,6-diamino-1,3,5-triazin-2-yl)prop-2-enamide Chemical compound NC1=NC(N)=NC(NC(=O)C=C)=N1 DHQIYHHEPUYAAX-UHFFFAOYSA-N 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
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- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、メタリック塗装に用いられる塗料に係り、更に詳細には、蒸着金属薄片などの光輝材の配向性が良好であり、金属的で意匠性に優れた外観を有するメタリック塗装を実現し得るメタリック塗料、メタリック塗膜及びメタリック塗膜の形成方法に関する。 The present invention relates to a paint used for metallic coating, and more specifically, the orientation of a bright material such as vapor-deposited metal flakes is good, and a metallic coating having a metallic and excellent appearance can be realized. The present invention relates to a metallic paint, a metallic coating film, and a method for forming a metallic coating film.
従来より、自動車車体のメタリック塗装においては、金属的な外観を発現させるべく、光輝材として光反射性の良好な蒸着アルミニウム薄片などを用いた塗装が行われてきたが、かかる光輝材を用いたメタリック塗料で金属のような意匠を実現しようとしても、小型製品や部品等の小さな被塗物でしか実現できておらず、自動車ボディにおける自動塗装のような広い面積で生産タクトの短い塗装では実質的に実現できていなかった。 Conventionally, in metallic coating of automobile bodies, coating using vapor-deposited aluminum flakes with good light reflectivity has been performed as a glittering material in order to develop a metallic appearance, but this glittering material was used. Even if we try to realize a metallic design with metallic paint, it can only be realized with small objects such as small products and parts, and it is practical for painting with a short production tact over a large area such as automatic painting in an automobile body. Could not be realized.
また、従来の自動車ボディ塗装ラインにおけるメタリック塗料及び塗装方法は、メタリック用ベル塗装機を用いて２ステージで１５μｍ程度の膜厚を塗装するものであるが、この際の塗料ＮＶ値（Ｎｏｎ Ｖｏｌａｔｉｌｅ値；不揮発固形分含有量）は２０％程度であり、かかる従来のメタリック塗料に反射性の強い蒸着アルミニウム薄片等を用いても、得られるメタリック塗装構造中での蒸着アルミニウム薄片の配向性が未だ十分とは言えず、金属的な意匠性が得られていなかった。 Further, the conventional metallic paint and painting method in the automobile body painting line is to paint a film thickness of about 15 μm in two stages using a metallic bell painting machine. In this case, the paint NV value (Non Volatile value) ; Non-volatile solid content) is about 20%, and even when highly reflective vapor-deposited aluminum flakes and the like are used in such a conventional metallic paint, the orientation of the vapor-deposited aluminum flakes in the resulting metallic coating structure is still sufficient However, metallic design was not obtained.
これに対し、本発明者らは、自動車等の塗装工程において光輝材の配向を制御する技術を開発し、２００２年４月１９日付けの特許出願にて、蒸着アルミ等を用いた金属調を有するメタリック塗装などを提案している（例えば、特許文献１参照）。
しかしながら、本発明者らが更に検討を加えたところ、上記特許出願に係るメタリック塗料やメタリック塗装にも更なる改良の余地があることが判明した。
即ち、この特許出願に係るメタリック塗装は、従来のメタリック塗装に比し優れた金属的意匠性を有するものであるが、Ｘ−Ｒｉｔｅ社のメタリック感指標であるＦＩ値は１８〜２０レベルである。これに対し、モーターショー等に出品される自動車に施されているメタリック塗装は、展示に特化された仕様であり、耐久性、耐候性、塗膜密着性及び耐チッピング性などに劣り実用に供するには不十分なものの、そのＦＩ値は２１レベル以上であり、金属そのものに近い意匠を有している。
このように、上記特許出願に係るメタリック塗料やメタリック塗装であっても、実用に供せる耐久性などの諸特性を有するメタリック塗装であって、ＦＩ値が２１レベル以上の金属自体に近い優れた意匠性を有する塗装を実際の製造ラインにおいて実現するには至っていないことが判明した。
However, as a result of further studies by the present inventors, it has been found that there is room for further improvement in the metallic paint and metallic coating according to the above patent application.
In other words, the metallic coating according to this patent application has an excellent metallic design compared to the conventional metallic coating, but the FI value, which is a metallic feeling index of X-Rite, is 18 to 20 levels. . On the other hand, the metallic paint applied to automobiles exhibited at motor shows, etc. is a specification that is specialized for the exhibition, and is inferior in durability, weather resistance, paint film adhesion and chipping resistance, etc. Although it is insufficient to provide, its FI value is 21 level or more, and it has a design close to that of the metal itself.
Thus, even metallic coatings and metallic coatings according to the above patent application are metallic coatings having various properties such as durability that can be put to practical use, and have an FI value close to that of the metal itself of 21 levels or more. It has been found that paint having design properties has not been realized in an actual production line.
本発明は、このような従来技術の有する課題に鑑みてなされたものであり、その目的とするところは、塗装構造中での光輝材の配向性が良好で、金属自体に近い外観を実現でき、しかも短時間で広い領域を塗装でき、優れた塗装効率を実現し得るメタリック塗料、塗膜及び塗膜形成方法を提供することにある。 The present invention has been made in view of such problems of the prior art, and the object of the present invention is that the orientation of the glittering material in the coating structure is good and an appearance close to the metal itself can be realized. Furthermore, an object of the present invention is to provide a metallic paint, a coating film and a coating film forming method capable of painting a wide area in a short time and realizing an excellent painting efficiency.
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、光輝材の配向性を左右する因子の解明が未だ十分ではなく、かかる因子の制御が不十分であることを知見し、塗料の塗着後の所定状態を適切に制御できるような配合組成を採用することなどにより、上記目的が達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the factors affecting the orientation of the glittering material are not yet fully elucidated, and that the control of such factors is insufficient, It has been found that the above object can be achieved by adopting a blending composition capable of appropriately controlling the predetermined state after the coating of the paint, and the present invention has been completed.
即ち、本発明のメタリック塗料は、固形分中１０〜３０％の光輝材と、固形分中１０〜５０％の分子量２５，０００〜５０，０００のセルロースアセテートブチレート樹脂と、残量としてのアクリル−メラミン樹脂を含有する塗料基材を含有するものであり、この塗料基材をエステル系溶剤及び／又はケトン系溶剤で固形分が１〜１０％となるような希釈率にて希釈して成るメタリック塗料であって、常温常圧の条件下、塗着から塗膜形成の間に、転球試験による転球所要時間が１０秒未満の未乾燥時間域と、転球所要時間が１０〜３０秒の粘度上昇時間域と、転球所要時間が３秒未満の指触乾燥時間域が順次存在し、上記転球所要時間の最大値が、上記粘度上昇時間域に存在し、且つ１５〜３０秒であることを特徴とする。
That is, the metallic paint of the present invention comprises a glittering material having a solid content of 10 to 30%, a cellulose acetate butyrate resin having a molecular weight of 25,000 to 50,000 in the solid content, and an acrylic resin as the remaining amount. -A paint base material containing a melamine resin is contained, and the paint base material is diluted with an ester solvent and / or a ketone solvent at a dilution rate such that the solid content becomes 1 to 10%. It is a metallic paint, and the time required for rolling by a rolling test is less than 10 seconds between coating and coating formation under normal temperature and pressure, and the rolling required time is 10-30. A viscosity increase time range of seconds and a finger touch drying time region where the rolling ball required time is less than 3 seconds are sequentially present, and the maximum value of the rolling ball time is present in the viscosity increasing time region, and 15 to 30 It is characterized by seconds .
また、本発明のメタリック塗膜は、上述の如きメタリック塗料を用いて形成されるメタリック塗膜であって、
固形分中１０〜３０％の光輝材と、固形分中１０〜５０％のセルロースアセテートブチレート樹脂と、残量としてのアクリル−メラミン樹脂を含有し、そのＦＩ値が２１以上である。
Moreover, the metallic coating film of the present invention is a metallic coating film formed using the metallic paint as described above,
It contains 10 to 30% of the glittering material in the solid content, 10 to 50% of the cellulose acetate butyrate resin in the solid content, and acrylic-melamine resin as the remaining amount, and its FI value is 21 or more.
更に、本発明のメタリック塗膜形成方法は、上述の如きメタリック塗料を用い、ベル型塗装機によって塗装する方法であるが、シェーピングエアー流量を４００〜８００Ｎｌ／ｍｉｎとすることが好ましい。 Furthermore, the method for forming a metallic coating film of the present invention is a method in which a metallic paint as described above is used and is applied by a bell-type coating machine, but the shaping air flow rate is preferably 400 to 800 Nl / min.
本発明によれば、塗料の塗着後の所定状態を適切に制御できるような配合組成を採用することなどとしたため、塗装構造中での光輝材の配向性が良好で、金属自体に近い外観を実現でき、しかも短時間で広い領域を塗装でき、優れた塗装効率を実現し得るメタリック塗料、塗膜及び塗膜形成方法を提供することができる。 According to the present invention, it is decided to adopt a blending composition that can appropriately control the predetermined state after the coating of the paint, so that the orientation of the glittering material in the coating structure is good and the appearance is close to the metal itself In addition, it is possible to provide a metallic paint, a coating film, and a coating film forming method capable of coating a wide area in a short time and realizing excellent coating efficiency.
以下、本発明のメタリック塗料につき詳細に説明する。なお、本明細書及び請求の範囲において、「％」は特記しない限り質量百分率を表すものとする。
上述の如く、本発明のメタリック塗料は、所定の塗料基材をエステル系溶剤及び／又はケトン系溶剤でその固形分が１〜１０％となるような希釈率にて希釈したものであり、この塗料基材は、固形分中、１０〜３０％の光輝材と、１０〜５０％のセルロースアセテートブチレート樹脂と、残量としてのアクリル−メラミン樹脂を含有する。
なお、この塗料基材において、光輝材、セルロースアセテートブチレート樹脂（以下、「ＣＡＢ樹脂」と略す）及びアクリル−メラミン樹脂は不揮発性固形分であって塗膜形成要素として機能し、ＣＡＢ樹脂はいわゆる粘性樹脂として機能する。
Hereinafter, the metallic paint of the present invention will be described in detail. In the present specification and claims, “%” represents a mass percentage unless otherwise specified.
As described above, the metallic paint of the present invention is obtained by diluting a predetermined paint base material with an ester solvent and / or a ketone solvent at a dilution rate such that the solid content is 1 to 10%. The coating material base contains 10 to 30% of a glittering material, 10 to 50% of cellulose acetate butyrate resin, and an acrylic-melamine resin as the remaining amount in the solid content.
In this paint substrate, the glittering material, cellulose acetate butyrate resin (hereinafter abbreviated as “CAB resin”) and acrylic-melamine resin are non-volatile solids and function as coating film forming elements. It functions as a so-called viscous resin.
図１に、本発明のメタリック塗料における塗膜形成のメカニズムを示す。
同図において、まず、光輝材１を含む飛行塗料粒子１０が被塗物２０の表面に塗着すると（図１（ａ））、その飛行速度、粒径及び塗料基材の希釈率などに応じて、塗料粒子１０は変形して偏平化するとともに、鱗片状の光輝材１はその平面部位が被塗物２０の表面と平行になるように配向しようとする。
塗着後、塗料１０は飛行速度などに起因する粒子変形エネルギーや粘度に応じて更に周囲に広がって未硬化膜を形成しようとし、これに応じて光輝材１も更に平行に配向しようとする（図１（ｂ））。
次いで、塗料１０の拡散が終了して塗料の未硬化膜が形成されると、塗料１０の被塗物へのセッティングが完了し（図１（ｃ）〜（ｄ））、しかる後、溶剤の蒸発に応じて、塗料未硬化膜が体積収縮する。これに応じて光輝材１はいっそう平行に配向し（図１（ｄ））、メタリック塗膜が完成する。
In FIG. 1, the mechanism of the coating film formation in the metallic coating material of this invention is shown.
In the figure, first, when the
After coating, the
Next, when the diffusion of the
本発明は、上述のようなメタリック塗膜形成過程において、特に塗料の被塗物へのセッティング時の初期（図１（ｃ）参照）に、光輝材を流動させないがウェットな状態に塗料を導き、その後の体積収縮による光輝材の平行配向を更に促進させることを主眼としており、また、これを実現できるような塗料組成や塗料性状を提案するものである。
かかる主眼点を塗料（塗膜）粘性の変化から観察すると、図２に示すような関係が得られる。
In the present invention, in the process of forming a metallic coating film as described above, particularly in the initial stage (see FIG. 1C) at the time of setting the coating material to the coating object, the coating material is brought into a wet state without flowing the glittering material. The present invention aims to further promote the parallel alignment of the glittering material by the subsequent volume shrinkage, and proposes a paint composition and paint properties that can realize this.
When such a principal point is observed from a change in the viscosity of the paint (coating film), the relationship as shown in FIG. 2 is obtained.
図２において、曲線Ａは本発明のメタリック塗料の一例における粘性の経時変化を示し、曲線Ｂは従来のメタリック塗料の一例における粘性の経時変化を示している。
なお、縦軸の転球所要時間は、図３に示すように、常温常圧下、Ａ４版サイズの中塗り塗装を施したブリキ板に供試塗料を１０μｍ塗布し、このブリキ板を５゜以下の所定角度θに傾けて配置した後、１１ｍｍφで５．５ｇの鉄球をブリキ板の頂上から静かに転がし、その所要時間を一定時間毎に時系列で測定したものである。
In FIG. 2, a curve A shows a change in viscosity with time in an example of a metallic paint of the present invention, and a curve B shows a change in viscosity with time in an example of a conventional metallic paint.
As shown in FIG. 3, the time required for rolling the ball on the vertical axis is 10 μm of the test paint applied to a tin plate coated with an A4 size intermediate coat at room temperature and normal pressure, and this tin plate is 5 ° or less. Then, an iron ball of 5.5 g with 11 mmφ was gently rolled from the top of the tin plate, and the required time was measured in a time series at regular intervals.
図２に示したように、本発明のメタリック塗料（曲線Ａ）では、代表的に、塗着から塗膜形成までに、転球所要時間が１０秒未満の未乾燥時間域と、１０〜３０秒の粘度上昇時間域と、３秒未満の指触乾燥時間域がこの順で存在し、しかも未乾燥時間域が塗着時から２分間以内で、粘度上昇時間域がその後３分間以内で、その後に、指触乾燥時間域となることが分かる。なお、本発明で着目する塗料の被塗物へのセッティング時の初期は、曲線Ａにおいて、粘度上昇時間域の初期に相当する。
これに対し、従来のメタリック塗料（曲線Ｂ）では、塗着後に転球所要時間が増大して粘度が上昇することはなく、しかも塗着後約１分経過後は粘度の下降も極めて緩やかである。よって、上述したような塗料セッティング時以降における光輝材の平行配向を生ずることもないのである。
As shown in FIG. 2, in the metallic paint (curve A) of the present invention, typically, the time required for rolling is less than 10 seconds from application to coating formation, A viscosity increase time range of 2 seconds and a touch dry time range of less than 3 seconds exist in this order, and the undried time range is within 2 minutes from the time of application, and the viscosity increase time range is within 3 minutes thereafter, It turns out that it becomes a finger touch drying time area after that. In addition, the initial stage when setting the paint to which attention is paid in the present invention on the workpiece corresponds to the initial stage of the viscosity increase time period in curve A.
On the other hand, in the conventional metallic paint (curve B), the required rolling ball time does not increase after coating and the viscosity does not increase, and after about 1 minute after coating, the viscosity decreases very slowly. is there. Therefore, the parallel alignment of the glitter material after the paint setting as described above does not occur.
なお、本発明のメタリック塗料においては、転球所要時間の最大値は、粘度上昇時間域に存在し、且つ１５〜３０秒であるが、２０〜３０秒であることが好ましく、２５〜３０秒であることが一層好ましい。
転球所要時間の最大値が１５秒未満では、既にベース塗膜表面が乾燥しており塗膜収縮時にアルミニウム等の光輝材が配向し難く、３０秒を超えると、塗膜の粘度自体が高く、この場合も光輝材が配向し難い。
In the metallic coating of the present invention, the maximum value of the rolling sphere duration is present increase in viscosity the time domain, is a and 15 to 30 seconds, preferably from 20 to 30 seconds, 25-30 seconds It is more preferable that
If the maximum time required for rolling is less than 15 seconds, the surface of the base coating is already dry, and the glittering material such as aluminum is difficult to align when the coating shrinks. If it exceeds 30 seconds, the viscosity of the coating is high. In this case, the glittering material is difficult to be oriented.
また、本発明のメタリック塗料は、初期状態（塗着前）において、代表的に不揮発固形分を全量で１〜１０％の割合で含む、即ちＮＶ値が１〜１０％であるが、未乾燥時間域におけるＮＶ値が２０〜３０％、好ましくは２５〜３０％であり、且つ粘度上昇時間域におけるＮＶ値が４０〜６０％、好ましくは５０〜５５％であることが望ましい。
未乾燥時間域におけるＮＶ値が２０％未満では、塗膜粘度が低く配向が自ら乱れてしまうことがあり、３０％を超えると、塗膜粘度上昇率が高すぎて光輝材の配向が十分に起こらないことがある。
また、粘度上昇時間域におけるＮＶ値が４０％未満では、塗膜粘度が上昇せず転球所要時間１５秒以下になってしまうことがあり、６０％を超えると、塗膜が乾燥して転球所要時間が１５秒よりも短くなってしまうことがある。
Further, the metallic paint of the present invention typically contains a non-volatile solid content in a proportion of 1 to 10% in the initial state (before application), that is, the NV value is 1 to 10%, but is not dried. The NV value in the time range is 20 to 30%, preferably 25 to 30%, and the NV value in the viscosity increase time range is 40 to 60%, preferably 50 to 55%.
If the NV value in the undried time region is less than 20%, the coating viscosity is low and the orientation may be disturbed by itself. If it exceeds 30%, the coating viscosity increase rate is too high and the orientation of the glittering material is sufficient. It may not happen.
If the NV value in the viscosity increase time range is less than 40%, the viscosity of the coating film may not increase, and the required rolling ball time may be 15 seconds or less. If the NV value exceeds 60%, the coating film dries and rolls. The ball required time may be shorter than 15 seconds.
次に、本発明のメタリック塗料に用いる成分につき説明する。
まず、塗料基材に含まれる光輝材としては、パール顔料や金属フレークを挙げることができ、特に蒸着法で形成された金属フレークが代表的であるが、反射性の良好さから蒸着アルミニウムフレークを好適に用いることができる。
また、このような光輝材は典型的には鱗片状をなすが、その大きさは最大長部位が１０〜１００μｍで、厚みが０．０１〜０．２μｍであることが好ましい。
最大長部位が１０μｍ未満では、十分な光の反射が得られないことがあり、１００μｍを超えると、塗料循環装置における光輝材の沈降性に問題が発生することがある。
一方、厚みが０．０１μｍ未満では、塗料循環での形状安定性に劣ることがあり、０．２μｍを超えると、光輝材一枚当たりの重量が重くなり、例えばアルミフレーク自体の枚数が制限されることがある。
なお、かかる光輝材の配合量は、塗料基材の１０〜３０％である。１０％未満では、光輝材表面の面積が小さく十分な光の反射が得られないことがあり、３０％を超えると、光輝材の量が多いため塗料循環時に光輝材の沈降等の問題が生ずることがある。
Next, components used in the metallic paint of the present invention will be described.
First, examples of the glittering material contained in the paint substrate include pearl pigments and metal flakes, and metal flakes formed by a vapor deposition method are typical, but vapor deposition aluminum flakes are preferred because of their good reflectivity. It can be used suitably.
In addition, such a glittering material typically has a scale-like shape, and it is preferable that the maximum length portion is 10 to 100 μm and the thickness is 0.01 to 0.2 μm.
If the maximum length portion is less than 10 μm, sufficient light reflection may not be obtained, and if it exceeds 100 μm, a problem may occur in the sedimentation property of the glittering material in the paint circulation device.
On the other hand, when the thickness is less than 0.01 μm, the shape stability in the circulation of the paint may be inferior, and when it exceeds 0.2 μm, the weight per glittering material becomes heavy, for example, the number of aluminum flakes itself is limited. Sometimes.
In addition, the compounding quantity of this luster material is 10 to 30% of a coating material base material. If it is less than 10%, the area of the surface of the glittering material is small and sufficient light reflection may not be obtained. If it exceeds 30%, the amount of glittering material is large, causing problems such as sedimentation of the glittering material during paint circulation. Sometimes.
また、ＣＡＢ樹脂は、いわゆる粘性樹脂として機能し、塗着後にエステル系溶剤やケトン系溶剤が蒸発するに従って粘性を強く発現する。
このように、塗着した塗料の溶剤成分が蒸発するにつれて粘性樹脂の粘性が発現するので、上述のように平行に配置された光輝材の流動が抑制され、これにより、金属に近い外観を有する塗装が得られ易くなる。
かかるＣＡＢ樹脂の分子量としては、２５，０００〜５０，０００のものを用いるが、２５，０００〜３５，０００が好ましく、２６，０００〜３４，０００が更に好ましく、２８，０００〜３２，０００がいっそう望ましい。
ＣＡＢ樹脂の分子量が２５，０００未満では、塗膜粘度が低く光輝材の配向が乱れてしまう。また、５０，０００を超えると、粘度が高すぎて光輝材が十分に配向できない。
なお、かかるＣＡＢ樹脂の配合量は、塗料基材の１０〜５０％である。１０％未満では、十分な粘性を発現できず、５０％を超えると、塗膜を硬化させるアクリル−メラミン樹脂が相対的に少なくなって塗膜密着性などの十分な性能が発揮できなくなる。
Further, the CAB resin functions as a so-called viscous resin, and strongly develops viscosity as the ester solvent or ketone solvent evaporates after coating.
Thus, since the viscosity of the viscous resin develops as the solvent component of the applied paint evaporates, the flow of the glittering material arranged in parallel as described above is suppressed, thereby having an appearance close to metal. It becomes easy to obtain the coating.
The molecular weight of the CAB resin is 25,000 to 50,000, preferably 25,000 to 35,000, more preferably 26,000 to 34,000, and 28,000 to 32,000. More desirable.
When the molecular weight of the CAB resin is less than 25,000, the coating film viscosity is low and the orientation of the glittering material is disturbed. On the other hand, if it exceeds 50,000, the viscosity is too high and the glittering material cannot be sufficiently oriented.
In addition, the compounding quantity of this CAB resin is 10 to 50% of a coating material base material. If it is less than 10%, sufficient viscosity cannot be exhibited, and if it exceeds 50%, the acrylic-melamine resin for curing the coating film is relatively reduced, and sufficient performance such as coating film adhesion cannot be exhibited.
更に、アクリル−メラミン樹脂は、主に塗膜を硬化させるものとして機能する。
かかるアクリル−メラミン樹脂の配合量は、塗料基材の残量、即ち、これに上述の光輝材とＣＡＢ樹脂を合算したものが１００％となるような量とする。
なお、本発明において、塗料基材には、上述のような成分以外にも、塗膜形成要素としての顔料や可塑剤、硬化剤、表面調整剤、沈降防止剤、付着付与剤及びタレ防止剤などの添加剤を添加することも可能であるが、この場合もアクリル−メラミン樹脂の配合量は、他の全ての成分とこのアクリル−メラミン樹脂とを合算したものが１００％となるような量でよい。
Furthermore, the acrylic-melamine resin mainly functions as a material for curing the coating film.
The blending amount of the acrylic-melamine resin is set so that the remaining amount of the coating material base, that is, the total of the above-described glittering material and CAB resin is 100%.
In the present invention, in addition to the components described above, the paint base material includes pigments, plasticizers, curing agents, surface conditioners, anti-settling agents, adhesion-imparting agents and anti-sagging agents as film-forming elements. It is also possible to add additives such as, but in this case as well, the blending amount of the acrylic-melamine resin is such that the total of all other components and this acrylic-melamine resin is 100% It's okay.
更にまた、エステル系溶剤及びケトン系溶剤は、上述した塗料基材の希釈剤として機能するが、具体的には、３−酢酸−メトキシ−ブチル、２−エタノールアセテート、アルキルベンゼン、酢酸エチル及びトルエンなどを主成分とするシンナーを挙げることができる。
上述の如く、本発明のメタリック塗料は、上記塗料基材をかかるエステル系溶剤若しくはケトン系溶剤又はこれらの混合溶剤で希釈したものであるが、その希釈率は塗料中の固形分を１〜１０％とするものである。
本発明では、かかる希釈率を採用することにより、塗着する塗料粒子（飛行粒子）の粘度を低下させて、被塗物表面での塗着粒子の変形を従来のメタリック塗装の場合と比較して強く起こし、塗料中のアルミ薄片などの蒸着金属薄片を被塗物表面に対して平行に近く配置させることができる（図１（ａ）参照）。
なお、希釈率が１０％を超えると、塗着時における塗料粒子の変形が十分に起こらず、１％未満では、塗装機の吐出量が増加してしまい、塗装ラインでは実質的に適用困難になる。
Furthermore, the ester solvent and the ketone solvent function as a diluent for the above-mentioned coating base material. Specifically, 3-acetic acid-methoxy-butyl, 2-ethanol acetate, alkylbenzene, ethyl acetate, toluene and the like Can be mentioned.
As described above, the metallic paint of the present invention is obtained by diluting the paint base material with such an ester solvent, a ketone solvent, or a mixed solvent thereof. %.
In the present invention, by adopting such a dilution rate, the viscosity of the coating particles (flying particles) to be applied is lowered, and the deformation of the coating particles on the surface of the object to be coated is compared with the case of the conventional metallic coating. The deposited metal flakes such as aluminum flakes in the paint can be arranged in parallel to the surface of the object to be coated (see FIG. 1A).
If the dilution rate exceeds 10%, the coating particles are not sufficiently deformed at the time of coating, and if it is less than 1%, the discharge amount of the coating machine increases, making it substantially difficult to apply in the coating line. Become.
次に、本発明のメタリック塗膜について説明する。
このメタリック塗膜は、上述ようなメタリック塗料を用いて形成されるものであり、１０〜３０％の光輝材と、１０〜５０％のセルロースアセテートブチレート樹脂と、残量としてのアクリル−メラミン樹脂を含み、ＦＩ値が２１以上のものである。
ここで、ＦＩ値は、上述の如くＸ−Ｒｉｔｅ社のメタリック感指標であるが、具体的には、次式（Ａ）
ＦＩ＝２．６９×｛（Ｌ１５゜−Ｌ１１０゜）１．１１／（Ｌ４５゜）０．８６｝…（Ａ）
（式中のＬ１５゜、Ｌ４５゜及びＬ１１０゜は、ＪＩＳに規定される標準光源Ｄ６５を光源とし、平板状の塗膜表面にそれぞれ１５゜、４５゜及び１１０゜の角度で入射させた際の反射光の強度を示す）で表される。
本発明のメタリック塗膜は、このＦＩ値が２１以上であるが、２３以上が更に好ましい。ＦＩ値が２１未満では、「まさに金属」という反射が得られない。
Next, the metallic coating film of the present invention will be described.
This metallic coating film is formed using the metallic paint as described above, and 10 to 30% of a glittering material, 10 to 50% of a cellulose acetate butyrate resin, and an acrylic-melamine resin as the remaining amount. And the FI value is 21 or more.
Here, the FI value is a metallic feeling index of X-Rite as described above, and specifically, the following formula (A)
FI = 2.69 × {(L 15 ° −L 110 ° ) 1.11 / (L 45 ° ) 0.86 } (A)
(L 15 ° in the formula, L 45 ° and L 110 DEG, the standard light source D 65 prescribed in JIS as a light source, 15 ° respectively on a flat film surface, incident at 45 ° and 110 ° angle The intensity of the reflected light when it is made to be expressed).
The metallic coating film of the present invention has an FI value of 21 or more, more preferably 23 or more. When the FI value is less than 21, the reflection of “exact metal” cannot be obtained.
なお、本発明のメタリック塗膜では、ベース塗膜表面から３μｍまでの深さの表層領域に９９．７％以上の上記光輝材が存在することが好ましく、これにより、いっそう優れた金属感外観を実現することができる。
また、同量のアルミニウム光輝材が３μｍ以上の深さに亘って存在するようになると、深さが大きくなるにつれて反射が弱くなり、６μｍではＦＩ値が１９を下回るようになってしまう。
In the metallic coating film of the present invention, it is preferable that 99.7% or more of the glittering material is present in a surface layer region having a depth of 3 μm from the surface of the base coating film, thereby further improving the metallic appearance. Can be realized.
Further, when the same amount of the aluminum glitter material is present over a depth of 3 μm or more, the reflection becomes weaker as the depth increases, and the FI value becomes less than 19 at 6 μm.
次に、本発明のメタリック塗膜の形成方法について説明する。
本発明のメタリック塗膜形成方法は、上述のようなメタリック塗料を用い、ベル型塗装機によって塗装する方法であり、このメタリック塗料をベル型塗装機で被塗物に吐出することにより、塗装を行う方法である。
ここで、ベル型塗装機は従来公知のものであれば十分であるが、そのシェーピングエアー流量を４００〜８００Ｎｌ／ｍｉｎとすることが好ましく、これにより、塗料粒子の飛散速度を確保し、塗着時の塗料粒子変形エネルギーを十分に付与することができる。
シェーピングエアー流量が４００Ｎｌ／ｍｉｎ未満では、塗料粒子の変形エネルギーが不十分となることがあり、８００Ｎｌ／ｍｉｎを超えると、塗装機側のエアー供給対応が難しくなる。
Next, the formation method of the metallic coating film of this invention is demonstrated.
The metallic coating film forming method of the present invention is a method in which a metallic paint as described above is used and is applied by a bell-type coating machine, and the metallic coating is applied to an object to be coated by a bell-type coating machine. How to do it.
Here, it is sufficient that the bell type coating machine is a conventionally known one, but the shaping air flow rate is preferably set to 400 to 800 Nl / min. It is possible to sufficiently impart the coating particle deformation energy at the time.
If the shaping air flow rate is less than 400 Nl / min, the deformation energy of the paint particles may be insufficient, and if it exceeds 800 Nl / min, it becomes difficult to cope with air supply on the coating machine side.
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
（実施例１）
光輝材として蒸着アルミペースト（最大長部位４０μｍ）を固形分中２０％、ＣＡＢ樹脂としてＣＡＢ３８１−０．５（商品名：ＥＡＳＴＭＡＮ社製、分子量３０，０００）を固形分中４９％、アクリル−メラミン樹脂（日本ペイント製）を固形分中３１％の割合にて配合し、これを酢酸エチルを用い固形分が３．６％となるように希釈し、本例のメタリック塗料を得た。
Example 1
Evaporated aluminum paste (maximum length part 40 μm) as solid material is 20% in solid content, CAB resin as CAB381-0.5 (trade name: EASTMAN, molecular weight 30,000) is 49% in solid content, acrylic-melamine Resin (manufactured by Nippon Paint) was blended at a ratio of 31% in the solid content, and diluted with ethyl acetate so that the solid content was 3.6% to obtain a metallic paint of this example.
（比較例１）
ＣＡＢ３８１−０．５の代わりにＣＡＢ５００−５樹脂（商品名：ＥＡＳＴＭＡＮ社製、分子量５７，０００）を用いた以外は、実施例１と同様の操作を繰り返し、本例のメタリック塗料を得た。
(Comparative Example 1)
Except for using CAB500-5 resin (trade name: manufactured by EASTMAN, molecular weight 57,000) instead of CAB381-0.5, the same operation as in Example 1 was repeated to obtain a metallic paint of this example.
［性能評価］
実施例１及び比較例１のメタリック塗料を用い、下記の条件下で塗装を行い、塗膜形成を行った。
得られた各例のメタリック塗膜につき、Ｘ−Ｒｉｔｅ社製のＦＩ値測定機（商品名；ＭＡ６８ ＩＩ）を用いＦＩ値を測定した。
また、被塗物への塗着後における塗料の粘性経時変化を、上述した転球試験（図３参照；角度θ＝３．６゜）にて評価し、得られた結果を図４に示す。
更に、各例の塗膜をレーザー顕微鏡（倍率１０００倍）で表面観察し、得られた結果を図５に示す。
[Performance evaluation]
Using the metallic paints of Example 1 and Comparative Example 1, coating was performed under the following conditions to form a coating film.
About the obtained metallic paint film of each example, FI value was measured using the FI value measuring machine (brand name; MA68 II) made from X-Rite.
Further, the change with time in the viscosity of the paint after application to the object to be coated was evaluated by the above-mentioned rolling test (see FIG. 3; angle θ = 3.6 °), and the obtained result is shown in FIG. .
Furthermore, the surface of the coating film of each example was observed with a laser microscope (magnification 1000 times), and the obtained results are shown in FIG.
下記の条件で２回塗装し、平均膜厚３μｍのベース塗膜を得た。
（塗装条件）
・塗装機；ＡＢＢメタリックベル型塗装機、カップ径φ＝７０
・塗装条件；吐出量１５０ｍｌ／ｍｉｎ、ベル回転数；２５ｋｒｐｍ
・シェーピングエアー流量；７００Ｎｌ／ｍｉｎ
・印加電圧；−６０ｋＶ、塗装線速；５４ｍ／ｍｉｎ
・塗り重ね回数；４回
・被塗物
日本ペイント製の中塗り塗装を３０μｍ施したブリキ板、ポリエステル−メラミン焼付タイプ、明度Ｎ＝６
ベース塗装後５分間室温にて放置し、日本油脂（株）製の商品名ベルコートＮｏ．６２００（アクリル−メラミン塗料）を用いエアスプレーガンにて３０μｍ厚のクリアー塗装を実施し、１４０℃で２０分間の焼付乾燥を行った。
Coating was performed twice under the following conditions to obtain a base coating film having an average film thickness of 3 μm.
(Painting conditions)
・ Coating machine: ABB metallic bell type coating machine, cup diameter φ = 70
・ Coating conditions: Discharge rate 150ml / min, bell rotation speed: 25krpm
・ Shaping air flow rate: 700 Nl / min
-Applied voltage: -60 kV, coating line speed: 54 m / min
・ Coating times: 4 times ・ Coating material Tin plate with intermediate coating of 30μm made by Nippon Paint, polyester-melamine baking type, lightness N = 6
Leave at room temperature for 5 minutes after the base coating, trade name Bell Coat No. Using 6200 (acryl-melamine paint), clear coating with a thickness of 30 μm was carried out with an air spray gun, followed by baking and drying at 140 ° C. for 20 minutes.
ＦＩ値の測定結果は、実施例１のメタリック塗膜が２３で、比較例１のメタリック塗膜が１８．７であり、実施例１では蒸着アルミが良好に配向したが、比較例１では配向が不十分であった。
また、図４に示すように、実施例１では、転球所要時間で４分経過後に２０秒のピークが見られたが、比較例１では、このようなピークをとる挙動は示されなかった。
更に、図５及び図６に示すように、実施例１では、蒸着アルミの９９．７％が深さ３μｍの範囲に分布していたが、比較例２では蒸着アルミの９９．７％が深さ６μｍの範囲に分布していた。
The measurement result of the FI value is 23 for the metallic coating film of Example 1 and 18.7 for the metallic coating film of Comparative Example 1. In Example 1, the deposited aluminum was well oriented, but in Comparative Example 1, the orientation was oriented. Was insufficient.
Further, as shown in FIG. 4, in Example 1, a peak of 20 seconds was observed after 4 minutes in the required rolling time, but in Comparative Example 1, the behavior of taking such a peak was not shown. .
Further, as shown in FIGS. 5 and 6, in Example 1, 99.7% of the deposited aluminum was distributed in a range of 3 μm in depth, but in Comparative Example 2, 99.7% of the deposited aluminum was deep. It was distributed in the range of 6 μm.
１ 光輝材
１０ 塗料粒子
２０ 被塗物
1
Claims (7)
常温常圧の条件下、塗着から塗膜形成の間に、転球試験による転球所要時間が１０秒未満の未乾燥時間域と、転球所要時間が１０〜３０秒の粘度上昇時間域と、転球所要時間が３秒未満の指触乾燥時間域が順次存在し、
上記転球所要時間の最大値が、上記粘度上昇時間域に存在し、且つ１５〜３０秒であることを特徴とするメタリック塗料。 10 to 30% by mass of a glittering material, 10 to 50% by mass of a cellulose acetate butyrate resin having a molecular weight of 25,000 to 50,000 (MWn), and a solid paint base material containing an acrylic-melamine resin as the remaining amount Is a metallic paint obtained by diluting at a dilution rate such that the solid content is 1 to 10% by mass using an ester solvent and / or a ketone solvent ,
Between coating and film formation under normal temperature and normal pressure conditions, the rolling time required by the rolling test is less than 10 seconds, and the viscosity increase time range is 10-30 seconds. And there are sequentially finger touch drying time areas where the rolling ball required time is less than 3 seconds,
A metallic paint characterized in that the maximum value of the required rolling time is in the viscosity increase time range and is 15 to 30 seconds.
固形分中１０〜３０質量％の光輝材と、固形分中１０〜５０質量％のセルロースアセテートブチレート樹脂と、残量としてのアクリル−メラミン樹脂を含有し、ＦＩ値が２１以上であることを特徴とするメタリック塗膜。 A metallic coating film formed using the metallic paint according to any one of claims 1 to 3 ,
It contains 10 to 30% by mass of a glittering material in the solid content, 10 to 50% by mass of the cellulose acetate butyrate resin in the solid content, and an acrylic-melamine resin as the remaining amount, and the FI value is 21 or more. Characteristic metallic coating.
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| JP2005162977A (en) * | 2003-12-05 | 2005-06-23 | Nissan Motor Co Ltd | Coating composition, coated film and method for forming coated film |
| DE102006022057B3 (en) * | 2006-05-11 | 2007-10-31 | Dürr Systems GmbH | Rotary atomizer`s application unit for use in varnishing machine, has surface layer, on which thin coating medium with specific film thickness is formed, where layer reduces boundary surface friction between medium and overflow surface |
| JP5735196B2 (en) * | 2008-09-11 | 2015-06-17 | 株式会社ファルテック | Radome and method for manufacturing radome |
| US10293619B2 (en) * | 2015-04-02 | 2019-05-21 | Canon Kabushiki Kaisha | Metallic image forming method |
| CA2994370C (en) | 2015-07-31 | 2020-12-22 | Kansai Paint Co., Ltd. | Multi-layer coating film formation method |
| JP6732624B2 (en) | 2015-10-15 | 2020-07-29 | 関西ペイント株式会社 | Glitter coating composition |
| WO2017175468A1 (en) | 2016-04-04 | 2017-10-12 | 関西ペイント株式会社 | Bright pigment dispersion and method for forming multilayer coating film |
| CA3044198C (en) | 2016-11-18 | 2022-12-06 | Kansai Paint Co., Ltd. | Method for forming multi-layer coating film |
| JP7077073B2 (en) | 2017-04-11 | 2022-05-30 | 関西ペイント株式会社 | Glitter paint composition |
| JP7402839B2 (en) * | 2021-06-28 | 2023-12-21 | 日本ペイント・オートモーティブコーティングス株式会社 | Water-based bright paint composition and painted board |
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| JPH0770483A (en) * | 1993-09-07 | 1995-03-14 | Nippon Oil & Fats Co Ltd | Coating composition |
| JPH11290770A (en) * | 1998-04-15 | 1999-10-26 | Nof Corp | Formation of coating film |
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| JPH0770483A (en) * | 1993-09-07 | 1995-03-14 | Nippon Oil & Fats Co Ltd | Coating composition |
| JPH11290770A (en) * | 1998-04-15 | 1999-10-26 | Nof Corp | Formation of coating film |
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