JP5382611B2 - Fine-particle-containing soft coating and laminated coating - Google Patents
Fine-particle-containing soft coating and laminated coating Download PDFInfo
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本発明は、耐擦傷性や耐汚染性が要求される自動車のボディ等の塗装に適用できる微粒子含有軟質塗膜用塗料を用いて成る微粒子含有軟質塗膜及び積層塗膜に係り、更に詳細には、所定の粒径を有する微粒子を含む微粒子含有軟質塗膜用塗料を用いて成る微粒子含有軟質塗膜及び積層塗膜に関する。 The present invention relates to a fine-particle-containing soft coating film and a laminated coating film that use a fine-particle-containing soft coating film that can be applied to the coating of automobile bodies and the like that require scratch resistance and contamination resistance. Relates to a fine particle-containing soft coating film and a multilayer coating film formed using a fine particle-containing soft coating film containing fine particles having a predetermined particle diameter.
近年、自動車車体の軽量化やデザイン自由度の拡大などを目的として、その外板部材の一部が金属からプラスチックに代替されつつある。このようなプラスチック部材には、通常、塗装が施されている。 In recent years, a part of the outer plate member is being replaced from metal to plastic for the purpose of reducing the weight of an automobile body and increasing the degree of design freedom. Such plastic members are usually painted.
例えば、シートモールディングコンパウンド（ＳＭＣ）やポリマーアロイ等の硬質プラスチック製のフェンダー部材やバックドア部材などには、プライマー塗装後、金属部材と同様の中塗り塗装と上塗り塗装が施されている。一方、耐屈曲性や耐衝撃性が要求されるバンパー部材やサイドシルスポイラー部材などは、ポリプロピレンやウレタン等の軟質プラスチック製であり、プライマー塗装後、軟質の上塗り塗料による塗装が施されている。 For example, a fender member or a back door member made of hard plastic such as sheet molding compound (SMC) or polymer alloy is subjected to intermediate coating and top coating similar to those of metal members after primer coating. On the other hand, bumper members and side sill spoiler members that are required to have bending resistance and impact resistance are made of soft plastics such as polypropylene and urethane, and are coated with a soft top coat after primer coating.
最近では、これらの塗装の耐擦傷性を向上させるために、硬質クリヤー又は軟質クリヤーの適用が検討されており、一部の自動車の外板には施されている（例えば、特許文献１参照）。 Recently, in order to improve the scratch resistance of these coatings, application of hard clear or soft clear has been studied, and is applied to the outer plate of some automobiles (see, for example, Patent Document 1). .
なかでも硬質クリヤーについては、従来は塗膜にフロスト感を与えるために塗料に添加されていたシリカなどの微粒子フィラーを更に微細化し、硬質クリヤー用塗料に添加することで、硬質クリヤーの硬度を上げる試みがされている。これは、微粒子フィラーを含有することによって硬度が増した硬質クリヤーを適用することで、更に塗装の耐擦傷性を向上させるものである。 In particular, for hard clear, the fine filler such as silica, which has been added to the paint to give a frosted feeling to the paint film, is further refined and added to the hard clear paint to increase the hardness of the hard clear. An attempt has been made. This is to further improve the scratch resistance of the coating by applying a hard clear whose hardness has been increased by containing a fine particle filler.
しかしながら、内部応力が大きい硬質クリヤーは、厚膜化するとクラックが発生し易くなるため、その硬質化には限界があり、十分な耐擦傷性が得られないという問題点があった。
一方、軟質クリヤーは、軟質化に伴って鳥糞、花粉、虫、泥、水しみ等の汚れ、酸性雨及びガソリン、ワックス等の薬品に対する耐性が低下するので、軟質化に限界があるため、同様に十分な耐擦傷性が得られないという問題点があった。
However, a hard clear with a large internal stress tends to generate cracks when it is thickened, so that there is a limit to the hardening and there is a problem that sufficient scratch resistance cannot be obtained.
On the other hand, soft clearing has a limit in softening because its resistance to chemicals such as bird droppings, pollen, insects, mud, water stains, acid rain, gasoline, wax, etc. decreases with softening, Similarly, there was a problem that sufficient scratch resistance could not be obtained.
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、優れた耐擦傷性を有し、且つクラック等が発生しにくいという軟質塗膜の本来の特性は維持しつつ、優れた耐汚染性及び耐薬品性をも有する軟質塗膜用塗料を用いて成る軟質塗膜及び積層塗膜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 the original of a soft coating film having excellent scratch resistance and being less prone to cracks and the like. An object of the present invention is to provide a soft coating film and a laminated coating film using a coating film for a soft coating film having excellent antifouling resistance and chemical resistance while maintaining the above characteristics.
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、水酸基、カルボキシル基及びアミノ基から成る群より選ばれた少なくとも１種の架橋基を有する樹脂と、メラミン樹脂、イソシアネート樹脂及びエポキシ樹脂から成る群から選ばれる少なくとも１種を含む硬化剤と、粒径１〜３００ｎｍのシリカ、アルミナのいずれか一方又は双方である微粒子とを含み、上記微粒子の含有量が、固形分の５〜３０質量％であり、溶剤系塗料、水系塗料又は粉体塗料であり、且つ、常乾型、焼付け型、紫外線硬化型又は電子線硬化型である微粒子含有軟質塗膜用塗料を用いて成る微粒子含有軟質塗膜であって、セルロース系樹脂、ポリオレフィン樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリカーボネート樹脂、ポリウレタン樹脂及びＡＢＳ樹脂から成る群から選ばれる少なくとも１種のポリマーと粒径１〜３００ｎｍの微粒子とを含み、伸び率が２０〜１００％、且つヤング率が５〜１０００Ｎ／ｍｍ ２ であり、ガラス転移点が−２０〜７５℃であり、架橋密度が０．００５〜０．００８ｍｏｌ／ｃｃであり、上記微粒子の含有量が、５〜３０質量％である構成とすることにより、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 a resin having at least one crosslinking group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group, a melamine resin, an isocyanate resin, and A curing agent containing at least one selected from the group consisting of epoxy resins, and fine particles that are one or both of silica and alumina having a particle diameter of 1 to 300 nm, and the content of the fine particles is 5 ~ 30% by mass, consisting of solvent-based paint, water-based paint or powder paint, and using a paint for fine coating film containing fine particles which is normally dry type, baking type, ultraviolet ray curable type or electron beam curable type Soft film containing fine particles, cellulose resin, polyolefin resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylic resin, polycarbonate Over preparative resin, and a particulate of at least one polymer and a particle size 1~300nm selected from the group consisting of polyurethane resin and ABS resin, 20-100% elongation rate, and Young's modulus 5~1000N / mm 2 And having a glass transition point of -20 to 75 ° C., a crosslinking density of 0.005 to 0.008 mol / cc, and a content of the fine particles of 5 to 30% by mass , The inventors have found that the above object can be achieved and have completed the present invention.
即ち、本発明の微粒子含有軟質塗膜は、水酸基、カルボキシル基及びアミノ基から成る群より選ばれた少なくとも１種の架橋基を有する樹脂と、メラミン樹脂、イソシアネート樹脂及びエポキシ樹脂から成る群から選ばれる少なくとも１種を含む硬化剤と、粒径１〜３００ｎｍのシリカ、アルミナのいずれか一方又は双方である微粒子とを含み、上記微粒子の含有量が、固形分の５〜３０質量％であり、溶剤系塗料、水系塗料又は粉体塗料であり、且つ、常乾型、焼付け型、紫外線硬化型又は電子線硬化型である微粒子含有軟質塗膜用塗料を用いて成る微粒子含有軟質塗膜であって、セルロース系樹脂、ポリオレフィン樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリカーボネート樹脂、ポリウレタン樹脂及びＡＢＳ樹脂から成る群から選ばれる少なくとも１種のポリマーと粒径１〜３００ｎｍの微粒子とを含み、伸び率が２０〜１００％、且つヤング率が５〜１０００Ｎ／ｍｍ ２ であり、ガラス転移点が−２０〜７５℃であり、架橋密度が０．００５〜０．００８ｍｏｌ／ｃｃであり、上記微粒子の含有量が、５〜３０質量％であることを特徴とする。 That is, fine particle-containing soft coating of the present invention, a hydroxyl group, a resin having at least one crosslinking group selected from the group consisting of carboxyl group and an amino group, selected from the group consisting of melamine resins, isocyanate resins and epoxy resins A hardener containing at least one selected from the above and fine particles which are either one or both of silica and alumina having a particle diameter of 1 to 300 nm, and the content of the fine particles is 5 to 30% by mass of the solid content, It is a solvent-based paint, water-based paint, or powder paint, and is a fine-particle-containing soft coating film that uses a paint for fine-particle-containing soft paint films that is normally dry, baked, ultraviolet curable, or electron beam curable. Cellulosic resin, polyolefin resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylic resin, polycarbonate resin, polyurethane And at least one of the fine particles of the polymer and the particle diameter 1~300nm selected from the group consisting of down resin and ABS resin, 20-100% elongation percentage, and the Young's modulus is 5~1000N / mm 2, glass The transition point is −20 to 75 ° C., the crosslinking density is 0.005 to 0.008 mol / cc, and the content of the fine particles is 5 to 30% by mass .
また、本発明の積層塗膜は、該軟質塗膜を備えることを特徴とする。 Moreover , the laminated coating film of this invention is equipped with this soft coating film, It is characterized by the above-mentioned.
本発明によれば、水酸基、カルボキシル基及びアミノ基から成る群より選ばれた少なくとも１種の架橋基を有する樹脂と、メラミン樹脂、イソシアネート樹脂及びエポキシ樹脂から成る群から選ばれる少なくとも１種を含む硬化剤と、粒径１〜３００ｎｍのシリカ、アルミナのいずれか一方又は双方である微粒子とを含み、上記微粒子の含有量が、固形分の５〜３０質量％であり、溶剤系塗料、水系塗料又は粉体塗料であり、且つ、常乾型、焼付け型、紫外線硬化型又は電子線硬化型である微粒子含有軟質塗膜用塗料を用いて成る微粒子含有軟質塗膜であって、セルロース系樹脂、ポリオレフィン樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリカーボネート樹脂、ポリウレタン樹脂及びＡＢＳ樹脂から成る群から選ばれる少なくとも１種のポリマーと粒径１〜３００ｎｍの微粒子とを含み、伸び率が２０〜１００％、且つヤング率が５〜１０００Ｎ／ｍｍ ２ であり、ガラス転移点が−２０〜７５℃であり、架橋密度が０．００５〜０．００８ｍｏｌ／ｃｃであり、上記微粒子の含有量が、５〜３０質量％である構成としたため、優れた耐擦傷性を有し、且つクラック等が発生しにくいという軟質塗膜の本来の特性は維持しつつ、優れた耐汚染性及び耐薬品性をも有する軟質塗膜及び積層塗膜を提供することができる。 According to the present invention, a resin having at least one cross-linking group selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group, and at least one selected from the group consisting of a melamine resin, an isocyanate resin and an epoxy resin are included. A hardener and fine particles which are either one or both of silica and alumina having a particle diameter of 1 to 300 nm, and the content of the fine particles is 5 to 30% by mass of the solid content. Or a powder coating, and a fine particle-containing soft coating film using a coating material for fine particle-containing soft coating film, which is a normally dry type, a baking type, an ultraviolet curable type or an electron beam curable type, and comprising a cellulose resin, Polyolefin resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylic resin, polycarbonate resin, polyurethane resin, and ABS tree And a fine of at least one polymer and a particle size 1~300nm selected from the group consisting of 20 to 100 percent elongation, and Young's modulus is 5~1000N / mm 2, a glass transition point of -20 -75 ° C, the crosslink density is 0.005-0.008 mol / cc, and the content of the fine particles is 5-30% by mass , so that it has excellent scratch resistance and cracks. inherent properties of the soft coating that like is unlikely to occur while maintaining, it is possible to provide a soft Shitsunurimaku and multilayer coating film that Yusuke also excellent stain resistance and chemical resistance.
以下、本発明に用いる微粒子含有軟質塗膜用塗料、本発明の微粒子含有軟質塗膜及び積層塗膜につき詳細に説明する。なお、本明細書において、濃度及び含有量等についての「％」は特記しない限り質量百分率を表すものとする。 Hereinafter, the fine particle-containing soft coating paint for use in the present invention will be described in detail microparticle-containing soft coating and multilayer coating film of the present invention. In this specification, “%” for concentration, content, etc. represents mass percentage unless otherwise specified.
上述の如く、本発明に用いる微粒子含有軟質塗膜用塗料は、少なくとも１種の架橋基を有する樹脂と、メラミン樹脂、イソシアネート樹脂及びエポキシ樹脂から成る群より選ばれた少なくとも１種を含む硬化剤と、粒径１〜３００ｎｍの微粒子を含む。
ここで「微粒子を含む」とは、一次粒子、二次粒子、三次粒子のいずれの形態かを問わず、微粒子が分散されている状態をいう。
As described above, the coating material for a fine coating film containing fine particles used in the present invention includes at least one resin having a crosslinking group and at least one selected from the group consisting of melamine resin, isocyanate resin and epoxy resin. And fine particles having a particle diameter of 1 to 300 nm.
Here, “including fine particles” means a state in which fine particles are dispersed regardless of the form of primary particles, secondary particles, or tertiary particles.
上記架橋基としては、例えば水酸基、カルボキシル基、アミノ基などの光架橋基を有する。上記樹脂はこれらの架橋基の１種又は複数種を有している。樹脂に含まれるこれらの架橋基が上記硬化剤と架橋反応することによって、該樹脂が造膜するものである。 As the crosslinking group, having for example, a hydroxyl group, a carboxyl group, an amino group of which photocrosslinking group. The resin has one or more of these crosslinking groups . When these crosslinking groups contained in the resin undergo a crosslinking reaction with the curing agent, the resin forms a film.
上記微粒子は、シリカ及びアルミナである。これらの微粒子は、単独で又は複数種を組み合わせて用いられる。また、これらの微粒子は、硬化剤と反応する水酸基等の官能基を有していても良く、塗料への分散性を向上させるために、ポリシロキサン等の処理が行なわれていても良い。 The microparticles are shea silica and alumina. These fine particles are used alone or in combination of two or more. These fine particles may have a functional group such as a hydroxyl group that reacts with the curing agent, and may be treated with polysiloxane or the like in order to improve dispersibility in the paint.
上述のように該微粒子の粒径は１〜３００ｎｍであるが、好ましくは１〜１００ｎｍ、より好ましくは１〜５０ｎｍであり、一次粒子、二次粒子及び三次粒子のいずれの状態であっても上記粒径範囲内にある。１ｎｍ未満では、塗膜を形成した際に耐汚染性や耐薬品性を向上させる効果が小さく、３００ｎｍを超えると形成した塗膜の透明性や、光沢、平滑性などの塗装外観が低下する。 As described above, the particle diameter of the fine particles is 1 to 300 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm, and the above state is in any state of primary particles, secondary particles, and tertiary particles. Within the particle size range. If it is less than 1 nm, the effect of improving stain resistance and chemical resistance is small when a coating film is formed, and if it exceeds 300 nm, the coating appearance such as transparency, gloss, and smoothness of the coating film is deteriorated.
塗膜中の微粒子により軟質塗膜自体の耐汚染性や耐薬品性が向上する作用機構は完全には明らかではないが、架橋反応による塗膜形成の際に、塗料に分散していたこれらの微粒子が架橋による編目構造の空間に入り込んで固定され、それらの微粒子によって、塗膜表面から進入する汚れや薬品の塗膜内部への浸透が遮断されることで実現していると考えることができる。
また塗膜上にクラックが発生した場合にも、上記微粒子の遮断効果によってクラックの進行を防止できる効果が期待される。
Although the mechanism of action that improves the stain resistance and chemical resistance of the soft coating film itself due to the fine particles in the coating film is not completely clear, these were dispersed in the paint during the formation of the coating film by the crosslinking reaction. It can be considered that the fine particles enter the space of the stitch structure by crosslinking and are fixed, and the fine particles block the penetration of dirt and chemicals entering from the coating surface into the coating film. .
In addition, even when a crack occurs on the coating film, an effect of preventing the progress of the crack is expected due to the above-described blocking effect of the fine particles.
微粒子の塗料中の含有量は、塗料に含まれる固形分のうち、５〜３０％であり、好ましくは５〜２０％であり、更に好ましくは１０〜１５％である。１％未満では耐汚染性や耐薬品性が低下する場合があり、３０％を超えると塗膜の凝集力が低下し、耐傷付き性が低下したり、耐衝撃性の低下によって割れが生じたりする場合がある。 Content in the coating of the microparticles, of the solids contained in the coating is from 5 to 30%, good Mashiku is 5-20%, more preferably 10 to 15%. If it is less than 1%, the stain resistance and chemical resistance may be reduced. If it exceeds 30%, the cohesive strength of the coating film will be reduced, the scratch resistance will be reduced, and cracks may be caused by the reduced impact resistance. There is a case.
本発明に用いる軟質塗膜用塗料は、溶剤系塗料、水系塗料又は粉体塗料の形態である。また、樹脂、硬化剤及び微粒子の他に、溶剤、添加剤、顔料等が含まれていてもよい。例えば、透明クリヤー用塗料では、溶剤、添加剤が、濁りクリヤー用塗料では、溶剤、添加剤、若干の顔料（通常、塗料固形分に対して５％以下）が、エナメル塗料、ベースコート塗膜及び下塗り塗膜用塗料では、溶剤、添加剤、顔料を含むことができる。 Soft coating paint for use in the present invention, solvent-based paints, Ru form der of water-based paints or powder coatings. In addition to the resin, the curing agent, and the fine particles, a solvent, an additive, a pigment, and the like may be included. For example, in clear clear paints, solvents and additives are used. In turbid clear paints, solvents, additives, and some pigments (usually 5% or less of the solid content of the paint) are used in enamel paints, base coat films and In the paint for undercoat films, a solvent, an additive, and a pigment can be included.
上記溶剤の具体例としては、酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、ジエチルエーテル、ジオキサン等のエーテル類、トルエン、キシレン、ソルベッソ（登録商標）等の炭化水素溶剤などを用いることができる。これらは２種以上を適宜混合しても良い。 Specific examples of the solvent include esters such as ethyl acetate, butyl acetate and isobutyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether and dioxane, toluene, xylene, Solvesso (registered trademark) and the like. These hydrocarbon solvents can be used. Two or more of these may be mixed as appropriate.
上記添加剤の具体例としては、分散剤、紫外線吸収剤、光安定化剤、表面調整剤、ワキ防止剤などを用いることができる。これらは２種以上を適宜混合しても良い。 Specific examples of the additive include a dispersant, an ultraviolet absorber, a light stabilizer, a surface conditioner, and a crack inhibitor. Two or more of these may be mixed as appropriate.
上記顔料の具体例としては、アゾ系顔料、フタロシアニン系顔料、ペリレン系顔料等の有機系着色顔料や、カーボンブラック、二酸化チタン、ベンガラ等の無機系着色顔料を用いることができる。これらは２種以上を適宜混合しても良い。 Specific examples of the pigment include organic color pigments such as azo pigments, phthalocyanine pigments, and perylene pigments, and inorganic color pigments such as carbon black, titanium dioxide, and bengara. Two or more of these may be mixed as appropriate.
本発明に用いる軟質塗膜用塗料の塗布方法としては、スプレー塗装やインモールドコーティング等を挙げることができるが、これらに限定されるものではない。また塗膜形成方法としては、室温乾燥、焼付け乾燥、紫外線硬化、電子線硬化等を挙げることができる。 Examples of the method for applying the coating material for soft coating used in the present invention include spray coating and in-mold coating, but are not limited thereto. Examples of the coating film forming method include room temperature drying, baking drying, ultraviolet curing, and electron beam curing.
形成される軟質塗膜の種類としては、透明クリヤー塗膜、濁りクリヤー塗膜、エナメル塗膜、ベースコート塗膜等があり、それぞれの塗膜の膜厚は特に限定されるものではないが、例えばクリヤー塗膜の膜厚は２０〜４０μｍ程度、エナメル塗膜の膜厚は２０〜４０μｍ程度、ベースコート塗膜の膜厚は１０〜２０μｍ程度、下塗り塗膜の膜厚は、２０〜４０μｍ程度が好ましい。 Examples of the soft coating film to be formed include a transparent clear coating film, a turbid clear coating film, an enamel coating film, a base coat coating film, etc., and the film thickness of each coating film is not particularly limited. The clear coating film thickness is preferably about 20 to 40 μm, the enamel coating film thickness is about 20 to 40 μm, the base coat coating film thickness is about 10 to 20 μm, and the undercoat coating film thickness is preferably about 20 to 40 μm. .
本発明の微粒子含有軟質塗膜は、上述の如く本発明に用いる軟質塗膜用の塗料を用いて成るものであり、セルロース系樹脂、ポリオレフィン樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリカーボネート樹脂、ポリウレタン樹脂及びＡＢＳ樹脂から成る群から選ばれる少なくとも１種のポリマーと粒径１〜３００ｎｍの微粒子とを含む。 The fine particle-containing soft coating film of the present invention is formed using the coating material for the soft coating film used in the present invention as described above, and is composed of a cellulose resin, a polyolefin resin, a polyester resin, a polyvinyl chloride resin, a polystyrene resin, acrylic resin, polycarbonate resin, at least one polymer and including a fine particle size 1~300nm selected from the group consisting of polyurethane resin and ABS resin.
塗膜中での微粒子の粒径は、塗料の場合と同様に１〜３００ｎｍであるが、好ましくは１〜１００ｎｍ、より好ましくは１〜５０ｎｍであり、一次粒子、二次粒子及び三次粒子のいずれの状態であっても上記粒径範囲内にある。１ｎｍ未満では、耐汚染性や耐薬品性を向上させる効果が小さく、３００ｎｍを超えると形成した塗膜の透明性や塗装外観が低下する。なお、上記粒径は、大塚電子株式会社 ゼータ電位・粒径測定システムＥＬＳＺ−２及び平板試料用セルを用いて測定した。 The particle size of the fine particles in the coating film is 1 to 300 nm as in the case of the paint, but preferably 1 to 100 nm, more preferably 1 to 50 nm, and any of primary particles, secondary particles, and tertiary particles. Even in this state, the particle size is within the above range. If it is less than 1 nm, the effect of improving the stain resistance and chemical resistance is small, and if it exceeds 300 nm, the transparency and the coating appearance of the formed coating film are deteriorated. In addition, the said particle size was measured using Otsuka Electronics Co., Ltd. zeta potential and the particle size measurement system ELSZ-2, and the cell for flat plate samples.
また、塗膜中の微粒子の含有量は、５〜３０％であり、好ましくは５〜２０％であり、更に好ましくは１０〜１５％である。塗料についての説明でも詳述したように、１％未満では耐汚染性や耐薬品性が低下する場合があり、３０％を超えると塗膜の凝集力が低下し、耐傷付き性が低下したり、耐衝撃性の低下によって割れが生じたりする場合があるからである。 The content of the fine particles in the coating film is from 5 to 30%, good Mashiku is 5-20%, more preferably 10 to 15%. As described in detail in the explanation of the paint, if it is less than 1%, the stain resistance and chemical resistance may decrease, and if it exceeds 30%, the cohesive strength of the coating film decreases and the scratch resistance decreases. This is because cracks may occur due to a decrease in impact resistance.
微粒子含有軟質塗膜の物性は、その伸び率が２０〜１００％、且つヤング率が５〜１０００Ｎ／ｍｍ２であることが好ましく、伸び率が５０〜１００％、且つヤング率が１００〜１０００Ｎ／ｍｍ２であることがより好ましく、伸び率が８０〜１００％、且つヤング率が５００〜１０００Ｎ／ｍｍ２であることが更に好ましい。伸び率が２０％未満であると耐傷付き性や耐衝撃性が低下することがあり、ヤング率が５Ｎ／ｍｍ２未満であると耐汚染性や耐薬品性が低下することがある。また伸び率が１００％を超えると耐汚染性や耐薬品性が低下することがあり、ヤング率が１０００Ｎ／ｍｍ２を超えると耐傷付き性や耐衝撃性が低下することがある。 Physical properties of the fine particle-containing soft coating, the elongation 20-100%, and preferably a Young's modulus of 5~1000N / mm 2, elongation of 50 to 100% and a Young's modulus of 100～1000N / more preferably mm 2, 80 to 100% elongation percentage, and the Young's modulus is more preferably 500~1000N / mm 2. If the elongation is less than 20%, the scratch resistance and impact resistance may be lowered, and if the Young's modulus is less than 5 N / mm 2 , the stain resistance and chemical resistance may be lowered. Further, if the elongation exceeds 100%, the stain resistance and chemical resistance may decrease, and if the Young's modulus exceeds 1000 N / mm 2 , the scratch resistance and impact resistance may decrease.
なお、上記伸び率及びヤング率は、フリーフィルムを株式会社東洋ボールドウイン製のＴＥＮＳＩＬＯＮ ＵＴＭ−４−２００を用いて室温で測定した。フィルムの引っ張り速度は、４ｍｍ／ｍｉｎで行った。 In addition, the said elongation rate and Young's modulus measured the free film at room temperature using Toyo Baldwin Co., Ltd. TENSILON UTM-4-200. The film pulling speed was 4 mm / min.
また、微粒子含有軟質塗膜のガラス転移点は、好ましくは−２０〜７５℃、より好ましくは０〜７５℃、更に好ましくは３０〜７５℃である。−２０℃未満であると耐汚染性や耐薬品性に対する効果が小さくなる場合があり、７５℃を超えると耐傷付き性や耐衝撃性が低下する場合がある。
なお、塗膜のガラス転移点は、フリーフィルムをセイコーインスツルメンツ株式会社製のＤＭＳ６１００を用いて動的粘弾性を測定し、主分散の損失正接（ｔａｎδ）のピーク温度から求めた。
The glass transition point of the fine particle-containing soft coating film is preferably -20 to 75 ° C, more preferably 0 to 75 ° C, and still more preferably 30 to 75 ° C. If it is less than -20 ° C, the effect on the stain resistance and chemical resistance may be reduced, and if it exceeds 75 ° C, scratch resistance and impact resistance may be lowered.
The glass transition point of the coating film was obtained from the peak temperature of the loss tangent (tan δ) of the main dispersion by measuring the dynamic viscoelasticity of the free film using DMS6100 manufactured by Seiko Instruments Inc.
更に、微粒子含有軟質塗膜の架橋密度は、０．００５〜０．００８ｍｏｌ／ｃｃである。
０．００１ｍｏｌ／ｃｃ未満であると、塗膜中に含有される微粒子が十分に架橋の網目構造の空間に固定されないため、進入した汚れや薬品の浸透が十分に遮断されない可能性があり、また塗膜自体が造膜しない可能性がある。０．０１ｍｏｌ／ｃｃを超えると塗膜が硬くなりすぎて、軟質塗膜の特性である耐擦傷性等が低下する可能性がある。
Furthermore, the crosslinking density of the particle-containing soft coating is 0.005 ~ 0.008 mol / c c.
If it is less than 0.001 mol / cc, the fine particles contained in the coating film are not sufficiently fixed in the space of the crosslinked network structure, so that there is a possibility that penetration of dirt and chemicals that have entered may not be sufficiently blocked. The coating film itself may not be formed. If it exceeds 0.01 mol / cc, the coating film becomes too hard, and the scratch resistance, which is a characteristic of the soft coating film, may be lowered.
上述のように本発明の微粒子含有軟質塗膜では、一定の粒径の微粒子を塗膜に分散することによって、耐汚染性や、耐薬品性を向上させているので、その軟質塗膜が本来有する伸び率、ヤング率、ガラス転移温度等の物性が大きく変化することはない。
従って、耐擦傷性や耐クラック性を損なうことなく、塗膜の軟質化によって低下するために軟質塗膜では期待されなかった耐汚染性や耐薬品性もが良好な軟質塗膜を得ることができる。
As described above, in the fine particle-containing soft coating film of the present invention, fine particles having a certain particle diameter are dispersed in the coating film to improve the stain resistance and chemical resistance. Physical properties such as elongation, Young's modulus, glass transition temperature and the like do not change significantly.
Therefore, without impairing the scratch resistance and crack resistance, it is possible to obtain a soft coating film with good stain resistance and chemical resistance, which was not expected with a soft coating film because it is lowered by the softening of the coating film. it can.
次に、本発明の積層塗膜について詳細に説明する。
本発明の積層塗膜は、本発明の微粒子含有軟質塗膜から成る塗膜層を１層以上備えるものであり、優れた耐擦傷性、耐クラック性、耐汚染性及び耐薬品性が要求される物品表面の被覆に好適に用いることができる。
Next, the laminated coating film of the present invention will be described in detail.
The laminated coating film of the present invention comprises at least one coating film layer comprising the fine particle-containing soft coating film of the present invention, and is required to have excellent scratch resistance, crack resistance, contamination resistance and chemical resistance. It can be suitably used for coating the surface of an article.
積層塗膜としては、被塗物に下塗り塗膜、ベースコート塗膜及びクリヤー塗膜を順次形成して成るものや、被塗物に下塗り塗膜、その上にエナメル塗膜を形成して成るものを実施形態として挙げることができる。下塗り塗膜は被塗物とベースコート塗膜やエナメル塗膜との密着性を向上させ、またエナメル塗膜は積層塗膜の耐擦傷性、耐チッピング性及び表面の平滑性を向上させるものである。一般にクリヤー塗膜は、ベースコート塗膜上には施されるが、エナメル塗膜には施されない。 Laminate coatings consist of an undercoat, basecoat and clear coatings that are sequentially formed on the object to be coated, and an undercoating film on the object to be coated, and an enamel film on it. Can be cited as an embodiment. The undercoat film improves the adhesion between the object to be coated and the base coat film or enamel film, and the enamel film improves the scratch resistance, chipping resistance and surface smoothness of the laminated film. . Generally, the clear coating is applied on the base coat coating, but not on the enamel coating.
被塗物としては、代表的には鉄、アルミ、銅などの各種金属材、ポリプロピレン、ポリカーボネートなどの各種有機材、石英、セラミックス（炭化カルシウム他）などの各種無機材が挙げられる。具体的な物品としては、耐擦傷性などが要求される自動車のボディ、メッキ、蒸着、スパッタリング等の処理が施されたアルミホイールやドアミラー、屋内・屋外における樹脂製品、階段、床、家具等の木工製品などを挙げることができる。
このようにして得られる塗装物品としては、自動車、オートバイ、自転車、鉄道、その他の運輸機、建設機械、携帯電話、電化製品、光学機器、家具、建材、楽器、鞄、スポーツ用品、レジャー用品、キッチン用品、ペット用品、文房具などを挙げることができる。
Typical examples of the objects to be coated include various metal materials such as iron, aluminum and copper, various organic materials such as polypropylene and polycarbonate, and various inorganic materials such as quartz and ceramics (calcium carbide, etc.). Specific articles include automobile bodies that require scratch resistance, aluminum wheels and door mirrors that have been subjected to plating, vapor deposition, sputtering, etc., indoor and outdoor resin products, stairs, floors, furniture, etc. Woodworking products can be listed.
Painted articles obtained in this way include automobiles, motorcycles, bicycles, railways, other transportation equipment, construction machinery, mobile phones, electrical appliances, optical equipment, furniture, building materials, musical instruments, bags, sports equipment, leisure goods, kitchens Goods, pet goods, stationery, etc.
ベースコート塗膜用、クリヤー塗膜用、エナメル塗膜用の塗料が溶剤系上塗り塗料である場合、これらの塗料を上述の被塗物に被覆する方法としては、公知慣用の方法、例えば、はけ塗り法、吹付け法、静電塗装法、電着塗装法、粉体塗装、スパッタ法等を用いることができる。また溶剤系上塗り塗料は、代表的には、加熱硬化（焼付け）処理により塗膜とすることができる。
なお、上記溶剤系上塗り塗料は、被塗物の全体又は一部に被覆できる。
When the coating for the base coat film, the clear coating film, or the enamel coating film is a solvent-based top coating, a method for coating these coatings on the above-mentioned coated object may be a known and conventional method such as brushing. A coating method, spraying method, electrostatic coating method, electrodeposition coating method, powder coating, sputtering method, or the like can be used. Further, the solvent-based top coating composition can be typically formed into a coating film by heat curing (baking) treatment.
In addition, the said solvent-type top coat can coat | cover the whole to-be-coated article or a part.
図１及び図２に本発明の積層塗膜の実施形態の一例の概略断面図を示す。
図１に示す積層塗膜は、下塗り塗膜層１０、ベースコート塗膜２０及びクリヤー塗膜４０から構成されている。クリヤー塗膜４０を本発明の微粒子含有軟質塗膜とし、この塗膜を形成する本発明に用いる微粒子含有軟質塗膜用塗料は硬化型溶剤系塗料とした。
FIG. 1 and FIG. 2 show schematic cross-sectional views of an example of an embodiment of the laminated coating film of the present invention.
The laminated coating film shown in FIG. 1 is composed of an undercoat
図２に示す積層塗膜は、下塗り塗膜層１０及びエナメル塗膜３０から構成されている。エナメル塗膜３０を本発明の微粒子含有軟質塗膜とし、この塗膜を形成する本発明に用いる微粒子含有軟質塗膜用塗料は硬化型溶剤系塗料とした。
なお、図１及び図２に示した微粒子含有軟質塗膜は、単独層には限定されず、複数の層から形成されていてもよい。
The laminated coating film shown in FIG. 2 includes an undercoat
The fine particle-containing soft coating shown in FIGS. 1 and 2 is not limited to a single layer, and may be formed from a plurality of layers.
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。 EXAMPLES Hereinafter, although a specific Example is given and this invention is demonstrated in detail, this invention is not limited by a following example.
（参考例１）
１．微粒子含有軟質塗料の調製
旭化成ケミカルズ株式会社製のポリカーボネートジオールＴ５６５０Ｊ（水酸基価；１４０ｍｇＫＯＨ／ｇ）を酢酸ブチルで５０％になるように溶解し、この溶液にＨＤＩ系イソシアネート（ＮＣＯ：１６．５％）を、上記ポリカーボネートジオールとイソシアネートとの割合が１．０／０．８となるように添加した溶液（Ａ）と、日本ポリウレタン工業株式会社製ポリエステルジオール ニッポラン５７１１（水酸基価；５５ｍｇＫＯＨ／ｇ）を酢酸ブチルで５０％になるように溶解し、この溶液にＨＤＩ系イソシアネート（ＮＣＯ：１６．５％）を、上記ポリエステルジオールとイソシアネートとの割合が１．０／０．２５となるように添加した溶液（Ｂ）とを割合が９／１となるように配合し、本例の軟質塗料とした。
( Reference Example 1)
1. Preparation of fine particle-containing soft paint Polycarbonate diol T5650J (hydroxyl value: 140 mgKOH / g) manufactured by Asahi Kasei Chemicals Corporation is dissolved with butyl acetate to a concentration of 50%, and HDI isocyanate (NCO: 16.5%) is dissolved in this solution. A solution (A) in which the ratio of the polycarbonate diol and the isocyanate is 1.0 / 0.8, and a polyester diol NIPPOLAN 5711 (hydroxyl value: 55 mgKOH / g) manufactured by Nippon Polyurethane Industry Co., Ltd. A solution obtained by dissolving 50% with butyl and adding HDI isocyanate (NCO: 16.5%) to this solution so that the ratio of the polyester diol and isocyanate is 1.0 / 0.25. (B) is blended so that the ratio is 9/1, and the soft coating of this example And the.
次いで、ビックケミー・ジャパン株式会社製のナノ粒子（製品名：ＮＡＮＯＢＹＫ−３６５０）を上記調製した塗料に、塗膜形成成分全量を基準として、１５％と成るように撹拌しながら添加した。 Next, nanoparticles (product name: NANOBYK-3650) manufactured by Big Chemie Japan Co., Ltd. were added to the prepared paint with stirring so as to be 15% based on the total amount of coating film forming components.
２．微粒子含有軟質塗膜の形成
リン酸亜鉛処理した厚み０．８ｍｍ、７０ｍｍ×１５０ｍｍのダル鋼板に、カチオン電着塗料（商品名「パワートップＵ６００Ｍ」、日本ペイント株式会社製カチオン型電着塗料）を、乾燥膜厚が２０μｍとなるように電着塗装した後、１６０℃で３０分間焼き付けた。
その後、ＢＡＳＦコーティングスジャパン株式会社製のグレーの下塗り（商品名：ハイエピコＮｏ．５００）を３０μｍ塗装し、１４０℃で３０分間焼き付けた。
2. Formation of soft coating film containing fine particles Cationic electrodeposition paint (trade name “Power Top U600M”, a cation type electrodeposition paint manufactured by Nippon Paint Co., Ltd.) is applied to a 0.8 mm thick, 70 mm × 150 mm thick steel sheet treated with zinc phosphate. After electrodeposition coating so that the dry film thickness was 20 μm, baking was performed at 160 ° C. for 30 minutes.
Thereafter, a gray undercoat (trade name: Hyepico No. 500) manufactured by BASF Coatings Japan Co., Ltd. was applied to 30 μm and baked at 140 ° C. for 30 minutes.
次いで、ＢＡＳＦコーティングスジャパン株式会社製のベルコートＮｏ．６０１０メタリック塗色を１０μｍ塗装し、ウエットオンウエットで微粒子含有軟質塗料を３０μｍ塗装し、１４０℃で３０分間焼き付けた。 Next, Bell Coat No. manufactured by BASF Coatings Japan Co., Ltd. A 6010 metallic coating color was applied by 10 μm, a fine particle-containing soft coating was applied by wet on wet at 30 μm, and baked at 140 ° C. for 30 minutes.
（参考例２、実施例３、実施例４、参考例５、実施例６、実施例７、参考例８、実施例９、実施例１０、比較例１〜５）
表１に示す仕様とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
（参考例２）
溶液（Ａ）／溶液（Ｂ）＝７／３とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
（実施例３）
溶液（Ａ）／溶液（Ｂ）＝５／５とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
（実施例４）
溶液（Ａ）／溶液（Ｂ）＝３／７とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
（参考例５）
溶液（Ａ）／溶液（Ｂ）＝１／９とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
（比較例２）
溶液（Ａ）／溶液（Ｂ）＝１０／０とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
（比較例３）
溶液（Ａ）／溶液（Ｂ）＝０／１０とした以外は、参考例１と同様の操作を繰返して、積層塗膜を形成した。
( Reference Example 2, Example 3, Example 4, Reference Example 5, Example 6, Example 7, Reference Example 8, Example 9, Example 10 , Comparative Examples 1 to 5)
Except for the specifications shown in Table 1, the same operation as in Reference Example 1 was repeated to form a laminated coating film.
( Reference Example 2)
A laminated coating film was formed by repeating the same operation as in Reference Example 1 except that Solution (A) / Solution (B) = 7/3.
(Example 3)
A laminated coating film was formed by repeating the same operation as in Reference Example 1 except that Solution (A) / Solution (B) = 5/5.
Example 4
A laminated coating film was formed by repeating the same operation as in Reference Example 1 except that Solution (A) / Solution (B) = 3/7.
( Reference Example 5)
A laminated coating film was formed by repeating the same operation as in Reference Example 1 except that Solution (A) / Solution (B) = 1/9.
(Comparative Example 2)
A laminated coating film was formed by repeating the same operation as in Reference Example 1 except that Solution (A) / Solution (B) = 10/0.
(Comparative Example 3)
A laminated coating film was formed by repeating the same operation as in Reference Example 1 except that Solution (A) / Solution (B) = 0/10.
（評価）
参考例１、参考例２、実施例３、実施例４、参考例５、実施例６、実施例７、参考例８、実施例９、実施例１０及び比較例１〜５の積層塗膜について、以下の（１）〜（５）の評価を行った。結果を表１及び表２に示す。
(Evaluation)
About the laminated coating film of Reference Example 1, Reference Example 2, Example 3, Example 4, Reference Example 5, Example 6, Example 7, Reference Example 8, Example 9, Example 10, and Comparative Examples 1-5 The following (1) to (5) were evaluated. The results are shown in Tables 1 and 2.
（１）耐汚染性
泥汚れ試験(泥成分含有汚染液塗布後、乾燥のサイクル試験後のスチーム洗浄)による明度差（ΔＬ）測定により、評価した。
◎：ΔＬ＜５．０
○：ΔＬ＜１０．０
△：ΔＬ＜１５．０
×：ΔＬ＜２０．０
(1) Contamination resistance It evaluated by the brightness difference ((DELTA) L) measurement by a mud dirt test (Steam washing | cleaning after a drying cycle test after applying a mud component containing contamination liquid).
A: ΔL <5.0
○: ΔL <10.0
Δ: ΔL <15.0
×: ΔL <20.0
（２）耐薬品性
ガソリン試験(無鉛レギュラーガソリンを滴下し、乾燥させた後、塗面を布で拭き取る)による、塗膜の軟化・膨潤の有無を確認した。
◎：変化なし
○：若干、塗膜が軟化
△：塗膜が軟化
×：塗膜が軟化し、膨潤している。
(2) Chemical resistance The presence or absence of softening / swelling of the coating film was confirmed by a gasoline test (dried unleaded regular gasoline was dried and then the coated surface was wiped with a cloth).
：: No change ○: Slightly softened coating film △: Softened coating film ×: Softened coating film and swollen
（３）耐擦傷性
磨耗試験機の摺動子にダストネル（摩擦布）を両面テープで貼り付け、０．２２ｇ／ｃｍ２の荷重下、微粒子含有ポリロタキサン塗膜上を５０回往復させ、傷の有無を目視評価した。
◎：傷がない。
○：殆ど傷がない。
△：少し傷がある。
×：目立つほど多くの傷がある。
(3) Abrasion resistance Dustnel (friction cloth) was attached to the slider of an abrasion tester with double-sided tape, and the microparticle-containing polyrotaxane coating film was reciprocated 50 times under a load of 0.22 g / cm2 to check for scratches. Was visually evaluated.
A: There is no scratch.
○: There is almost no scratch.
Δ: Slightly scratched
X: There are many scratches so as to be conspicuous.
（４）塗装外観
微粒子含有ポリロタキサン塗膜の平滑度合いを目視評価した。
◎：かなり平滑
○：若干、凹凸
△：凹凸
×：艶がない
(4) Paint appearance The degree of smoothness of the fine particle-containing polyrotaxane coating film was visually evaluated.
◎: Very smooth ○: Slightly uneven Δ: Uneven
表１及び表２の結果から明らかなように、本発明の実施例３、４、６、７、９、１０は比較例１〜５と比較して各評価項目の結果のバランスが良い。即ち、各々の項目について×の評価がなく、且つ△の評価となった項目が２つ以下である。
これらの結果は、規定の粒径の微粒子を軟質塗膜層に含有させることによって、耐汚染性、耐薬品性及び耐擦傷性の性能と外観とが総合的に良好な塗膜が得られることを示す。
As is apparent from the results of Tables 1 and 2, Examples 3, 4, 6, 7, 9, and 10 of the present invention have a better balance of the results of the evaluation items than Comparative Examples 1 to 5. That is, there is no evaluation of x for each item, and there are two or less items that are evaluated as Δ.
These results show that the inclusion of fine particles with a specified particle size in the soft coating layer makes it possible to obtain a coating film with excellent overall stain resistance, chemical resistance, and scratch resistance performance and appearance. Indicates.
１０ 下塗り塗装
２０ ベースコート塗装（メタリック塗装）
３０ 微粒子含有軟質塗膜（エナメル塗装）
４０ 微粒子含有軟質塗膜（クリヤー塗装）
10
30 Soft coating containing fine particles (enamel coating)
40 Soft coating film containing fine particles (clear coating)
Claims (4)
上記微粒子の含有量が、固形分の５〜３０質量％であり、
溶剤系塗料、水系塗料又は粉体塗料であり、且つ、常乾型、焼付け型、紫外線硬化型又は電子線硬化型である微粒子含有軟質塗膜用塗料を用いて成る微粒子含有軟質塗膜であって、
セルロース系樹脂、ポリオレフィン樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリカーボネート樹脂、ポリウレタン樹脂及びＡＢＳ樹脂から成る群から選ばれる少なくとも１種のポリマーと粒径１〜３００ｎｍの微粒子とを含み、
伸び率が２０〜１００％、且つヤング率が５〜１０００Ｎ／ｍｍ ２ であり、
ガラス転移点が−２０〜７５℃であり、
架橋密度が０．００５〜０．００８ｍｏｌ／ｃｃであり、
上記微粒子の含有量が、５〜３０質量％である
ことを特徴とする微粒子含有軟質塗膜。 A resin having at least one cross-linking group selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group ; a curing agent containing at least one type selected from the group consisting of a melamine resin, an isocyanate resin and an epoxy resin; silica 1 to 300 nm, and a particle which is either or both of the alumina seen including,
The content of the fine particles is 5 to 30% by mass of the solid content,
It is a solvent-based paint, water-based paint, or powder paint, and is a fine-particle-containing soft coating film that uses a paint for fine-particle-containing soft paint films that is normally dry, baked, ultraviolet curable, or electron beam curable. And
Cellulose resin, polyolefin resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylic resin, polycarbonate resin, polyurethane resin, and at least one polymer selected from the group consisting of ABS resin and fine particles having a particle size of 1 to 300 nm Including
The elongation is 20 to 100% and the Young's modulus is 5 to 1000 N / mm 2 .
The glass transition point is -20 to 75 ° C,
The crosslink density is 0.005 to 0.008 mol / cc,
The content of the fine particles is 5 to 30% by mass.
A soft coating film containing fine particles .
上記微粒子の含有量が、５〜２０質量％であるThe content of the fine particles is 5 to 20% by mass.
ことを特徴とする請求項１に記載の微粒子含有軟質塗膜。The fine particle-containing soft coating film according to claim 1.
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| JP5992251B2 (en) | 2012-08-21 | 2016-09-14 | 株式会社Adeka | Additive for automobile paint comprising modified silica composition |
| JP5696735B2 (en) | 2013-03-25 | 2015-04-08 | 日油株式会社 | Urethane curable composition |
| JP5997793B2 (en) * | 2014-03-26 | 2016-09-28 | 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 | Intermediate coating composition, multilayer coating film and method for forming this multilayer coating film |
| CN113025153A (en) * | 2021-03-04 | 2021-06-25 | 中国林业科学研究院木材工业研究所 | Flame-retardant coating and preparation method and application thereof |
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