JP2006265381A - Pigment with diffraction grating and method for preparing the same - Google Patents
Pigment with diffraction grating and method for preparing the same Download PDFInfo
- Publication number
- JP2006265381A JP2006265381A JP2005085813A JP2005085813A JP2006265381A JP 2006265381 A JP2006265381 A JP 2006265381A JP 2005085813 A JP2005085813 A JP 2005085813A JP 2005085813 A JP2005085813 A JP 2005085813A JP 2006265381 A JP2006265381 A JP 2006265381A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- diffraction grating
- resin
- diffraction
- coating film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000000034 method Methods 0.000 title claims description 14
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- 239000011347 resin Substances 0.000 claims abstract description 67
- 239000002245 particle Substances 0.000 claims abstract description 12
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
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- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
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- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、塗料や樹脂組成物などに配合して、それらに虹色の光輝性を付与する回折格子顔料及びその製造方法に関する。 The present invention relates to a diffraction grating pigment that is blended in a paint, a resin composition, or the like and imparts iridescence to them, and a method for producing the same.
ある一定の間隔（数μｍ）を有する回折格子に光が入射するとその反射光は分光され、虹色を発色する。最近、この光の回折原理を顔料に応用したものがいくつか提案され、これまでにはない全く新しい意匠効果が生まれている。 When light is incident on a diffraction grating having a certain interval (several μm), the reflected light is dispersed to produce a rainbow color. Recently, several proposals have been made that apply this light diffraction principle to pigments, and an entirely new design effect has been born.
塗膜や成型物に虹色を付与する回折格子顔料についてはいくつか知られている。例えば、フィルム等のシート上に剥離可能な樹脂層を配置し、この樹脂層に回折格子のパターンを転写し、さらに真空蒸着等によりアルミニウム等の金属層を配置することによって虹色の意匠効果を実現し、剥離、粉砕、分級によって顔料化を実現している（特許文献１参照）。また、溶融複合紡糸技術により高屈折率ポリマーと低屈折率ポリマーを交互に精密に積層した多層干渉性顔料の製造方法も開示されている（特許文献２参照）。 Several diffraction grating pigments that impart a rainbow color to a coating film or molded product are known. For example, by placing a peelable resin layer on a sheet such as a film, transferring a diffraction grating pattern to the resin layer, and further arranging a metal layer such as aluminum by vacuum deposition or the like, the rainbow-colored design effect can be obtained. Realization and pigmentation is realized by peeling, grinding and classification (see Patent Document 1). Also disclosed is a method for producing a multilayer interference pigment in which a high refractive index polymer and a low refractive index polymer are alternately and precisely laminated by a melt composite spinning technique (see Patent Document 2).
これらの光輝性顔料は、外部からの入射光をその表面で反射して虹色に輝き、塗料に配合されれば塗膜に、インキ組成物であれば描線または印刷面に、あるいは樹脂組成物であれば樹脂成型品の表面に、それら各種素地の色調と相まって変化に富んだ美粧性に優れた独特な外観を与える。また、この美粧性の向上を目的として、自動車、オートバイ、ＯＡ機器、携帯電話、家庭電化製品、印刷物または筆記用具類など各種用途に光輝性顔料は広く利用されている。 These brilliant pigments reflect incident light from the outside and shine in a rainbow color. If blended in a paint, they are applied to a coating film. If an ink composition, they are drawn on a printed surface or a resin composition. If so, the surface of the resin molded product is given a unique appearance with a variety of cosmetics and excellent cosmetics in combination with the colors of the various substrates. Further, for the purpose of improving the cosmetics, glitter pigments are widely used in various applications such as automobiles, motorcycles, OA equipment, mobile phones, home appliances, printed matter, writing instruments and the like.
しかし、上記のような従来の回折格子顔料の最大の問題点は量産性であり、シートから剥離させる工程や真空蒸着工程など複雑な工程を必要とする。この結果、顔料価格としては非常に高価なものとなってしまっており（１００万円／ｋｇ以上）、意匠効果には優れるものの汎用的には使用することができないのが実状であった。さらに、屈折率差が十分ではないため、発色強度に改善の余地がある。 However, the biggest problem of the conventional diffraction grating pigment as described above is mass productivity, which requires complicated processes such as a process of peeling from a sheet and a vacuum deposition process. As a result, the price of the pigment has become very expensive (1 million yen / kg or more), and although it has an excellent design effect, it cannot be used for general purposes. Furthermore, since the difference in refractive index is not sufficient, there is room for improvement in color development intensity.
上記問題点を解決するために１番目の発明によれば、内部が中空となっている樹脂製の粒子からなり、この中空部により回折格子が構成されていることを特徴とする回折格子顔料が提供される。 In order to solve the above problems, according to a first aspect of the invention, there is provided a diffraction grating pigment comprising resin particles having a hollow inside, wherein the diffraction grating is constituted by the hollow portion. Provided.
上記問題点を解決するために２番目の発明によれば、第一の樹脂により前記中空部の形状に相当する凹凸形状の面を有する成形体を形成し、第二の樹脂により前記成形体を完全に被覆して糸状物を形成し、前記第一の樹脂を除去して前記糸状物内を中空とし、前記糸状物を切断し、切断面を封止することの工程を含む、上記の回折格子顔料の製造方法が提供される。 In order to solve the above problems, according to the second invention, a molded body having an uneven surface corresponding to the shape of the hollow portion is formed by the first resin, and the molded body is formed by the second resin. The diffraction described above, comprising the steps of completely covering to form a filamentous material, removing the first resin to make the interior of the filamentous material hollow, cutting the filamentous material, and sealing the cut surface A method of making a lattice pigment is provided.
本発明によれば、従来のものに比べはるかに安価かつ大量に回折格子顔料を製造することを可能とし、回折格子顔料の汎用性を大きく高めることができる。さらには、この回折格子顔料はより高い発色強度を達成することができる。 According to the present invention, it is possible to produce a diffraction grating pigment in a much cheaper and large amount compared with the conventional one, and the versatility of the diffraction grating pigment can be greatly enhanced. Furthermore, this diffraction grating pigment can achieve higher color intensity.
本発明の回折格子顔料は樹脂製の粒子からなり、その内部が中空となっており、この中空部により回折格子が構成されていることを特徴とする。回折格子顔料を形成する材料として用いられる樹脂としては、成形が可能であれば特に制限されない。例えば、ポリエチレン、ポリプロピレン、エチレン−プロピレンコポリマー、ポリメチルペンテン、ポリスチレン、ＡＢＳ、ＡＳ、ＡＥＳ、アクリル樹脂、メタクリル樹脂、ポリアミド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリイミド、ポリアリレート、ポリアセタール、ポリカーボネート、ポリフェニレンエーテル、ポリスルホン、ポリフェニレンスルフィド、ポリエーテルサルホンまたはポリブタジエン、あるいはこれらポリマーの共重合体、混合物または変性物などが挙げられる。これらの中で、アクリル樹脂、メタクリル樹脂（例えばポリメチルメタクリレート、ＰＭＭＡ）、ポリスチレン、ポリエチレンテレフタレート、ポリカーボネート及びポリアミドは透明性が高いことから、本発明の回折格子顔料を形成する樹脂として好ましい。 The diffraction grating pigment of the present invention is made of resin particles, the inside of which is hollow, and the diffraction grating is constituted by the hollow portion. The resin used as a material for forming the diffraction grating pigment is not particularly limited as long as it can be molded. For example, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polystyrene, ABS, AS, AES, acrylic resin, methacrylic resin, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyarylate, polyacetal, polycarbonate, polyphenylene ether, Polysulfone, polyphenylene sulfide, polyethersulfone or polybutadiene, or a copolymer, mixture or modified product of these polymers may be mentioned. Among these, acrylic resin, methacrylic resin (for example, polymethyl methacrylate, PMMA), polystyrene, polyethylene terephthalate, polycarbonate, and polyamide are preferable as the resin for forming the diffraction grating pigment of the present invention because of their high transparency.
本発明の回折格子顔料の形状は、使用用途によって多少異なるが、一般的には溶融紡糸法によって製造された糸状物を、延伸、裁断して製造されるため、図１に示すように、楕円柱状の粒子１であり、断面の長径ｌが１０〜１００μｍであり、短径ｓが０．３〜１０μｍであり、厚みｔが１０〜１００μｍであることが好ましい。
The shape of the diffraction grating pigment of the present invention is somewhat different depending on the application, but is generally produced by stretching and cutting a filamentous material produced by a melt spinning method. Therefore, as shown in FIG. It is the
この粒子１中の中空部は、凹凸形状の面が所定の隙間をおいて相対することにより構成されており、回折格子として機能する。この凹凸形状の面上の凸部の頂点間の距離ｄは、顔料粒子１の幅（長径ｌ）の半分以下であることが好ましい。この距離ｄが顔料粒子１の幅（長径ｌ）の半分を超えると、中空部により構成される回折格子は平面に近づき、回折による分光幅が狭くなり、鮮明な虹を呈しなくなる。この距離ｄはより好ましくは１〜５μｍである。
The hollow portion in the
ここで図２を用いて、一般的な回折像の強度と回折角について説明する。図２に示すように、スリットの隙間を２ξ0、スリットのピッチをｄ、スリットとスクリーンの間の距離をｆとした場合、スリットに対して入射角θ0で入射した光は回折され、Ｎ次の回折光（Ｎ次光）は、スクリーン上で入射角θ0に対してＮ次の回折光の回折角θNの位置、すなわちスクリーン上の入射光の位置より距離ｘ離れた位置に現れる。このときの回折像の強度は、以下に示す式(1)により求めることができる。
ここで１本のスリットにおける回折像は、ｐ＝ｍλ／２ξ0のときに暗くなり、一方Ｍ重スリットによるヤングの干渉縞は、ｐ＝Ｎλ／ｄのときに明るくなる。また距離ｘとｆとの関係は、以下に示す式(2)の通りである。
ｐ＝ｘ／ｆ＝sinθN−sinθ0 (2)
θ0：入射角
θN：Ｎ次の回折光の回折角
Here, the diffraction image in one slit becomes dark when p = mλ / 2ξ 0 , while Young's interference fringes due to the M-fold slit become bright when p = Nλ / d. The relationship between the distances x and f is as shown in the following formula (2).
p = x / f = sinθ N −sinθ 0 (2)
θ 0 : Incident angle θ N : Diffraction angle of Nth order diffracted light
上記から、回折光の最大強度をＮ次の回折光の位置にするための条件は以下に示す式(3)より求めることができる。
sinθN−sinθ0＝Ｎλ／ｄ (3)
From the above, the condition for setting the maximum intensity of the diffracted light to the position of the Nth order diffracted light can be obtained from the following equation (3).
sinθ N −sinθ 0 = Nλ / d (3)
同様に、図３に示すような反射型の場合にも上記の式より説明することができ、回折光における干渉できる位置は距離ｄにより決まり、強度はξ／ｄで決まる。そして本発明の回折格子顔料における回折も、上記の回折像と同様に説明することができる。従って式(3)に示す式を用いて１次光を最大強度とする場合、Ｎ＝１として、顔料の凸部の頂点間の距離ｄと入射光の波長λと入射角度θ0とを入力することによって、１次光の回折角θNの位置を算出することができる。これにより、所望の虹色を呈する顔料の形状をあらかじめデザインすることができる。 Similarly, in the case of a reflection type as shown in FIG. 3, it can be explained by the above formula, and the position where interference in the diffracted light can be determined is determined by the distance d, and the intensity is determined by ξ / d. The diffraction in the diffraction grating pigment of the present invention can also be explained in the same manner as the above diffraction image. Therefore, when the primary light is set to the maximum intensity using the equation (3), N = 1 and the distance d between the vertices of the convex portions of the pigment, the wavelength λ of the incident light, and the incident angle θ 0 are input. By doing so, the position of the diffraction angle θ N of the primary light can be calculated. Thereby, the shape of the pigment which exhibits a desired rainbow color can be designed in advance.
１次回折光の回折角は、上記式(3)を用いて算出すると以下のようになる。
１次回折光の場合としてＮ＝−１を代入して
sin(α−２γ)−sinα＝−λ／ｄ
また、正反射の位置以外に出る波長については、
sinβ−sinα＝−λ／ｄ
よって、β＝sin−１（sinα−λ／ｄ）
従って、例えば入射角＝３０°、距離ｄ＝3000nmの場合、上記式より
波長λ＝ｄ（sinα−sin(α−２λ))
＝3000（sin30−sin20）
＝474nm
となる。また、他の波長の色の出る反射角は
β＝sin−１（sinα−λ／ｄ）
より求めることができ、以下の結果が得られる。
波長λ＝400nm→回折光の反射角β＝２２°
波長λ＝500nm→回折光の反射角β＝１９°
波長λ＝600nm→回折光の反射角β＝１７°
波長λ＝700nm→回折光の反射角β＝１５°
波長λ＝800nm→回折光の反射角β＝１３°
The diffraction angle of the first-order diffracted light is calculated as follows using the above formula (3).
Substituting N = -1 for the case of the first-order diffracted light
sin (α-2γ) −sinα = −λ / d
In addition, about the wavelength that goes out of the regular reflection position,
sin β−sin α = −λ / d
Therefore, β = sin−1 (sin α−λ / d)
Therefore, for example, when the incident angle = 30 ° and the distance d = 3000 nm, the wavelength λ = d (sin α−sin (α−2λ))
= 3000 (sin30−sin20)
= 474nm
It becomes. In addition, the reflection angle at which colors of other wavelengths appear is β = sin−1 (sin α−λ / d)
The following results can be obtained.
Wavelength λ = 400 nm → Diffraction light reflection angle β = 22 °
Wavelength λ = 500 nm → diffracted light reflection angle β = 19 °
Wavelength λ = 600 nm → diffracted light reflection angle β = 17 °
Wavelength λ = 700 nm → diffracted light reflection angle β = 15 °
Wavelength λ = 800 nm → diffracted light reflection angle β = 13 °
本発明の回折格子顔料では、内部の回折格子部が空気を含む中空となっている。空気層の屈折率はほぼ1.0であるため、粒子を構成する樹脂を選択することにより屈折率差を大きくすることができる。例えばポリエチレンテレフタレートの屈折率は１．５８、ポリカーボネートの屈折率は１．５９、ポリスチレンの屈折率は１．５９、ポリアミド（ナイロン）の屈折率は１．５３、ポリメチルメタクリレートの屈折率は１．４９であり、これらを樹脂材料として用いて上記のような回折格子顔料を製造することにより屈折率差を０．５程度と大きくすることができる。従来の回折格子顔料ではこの屈折率差は０．１〜０．２程度であり、光学理論的には、本発明の回折格子顔料は従来のものと比較して反射強度を５倍以上にすることができる。 In the diffraction grating pigment of the present invention, the internal diffraction grating portion is hollow containing air. Since the refractive index of the air layer is approximately 1.0, the refractive index difference can be increased by selecting the resin constituting the particles. For example, the refractive index of polyethylene terephthalate is 1.58, the refractive index of polycarbonate is 1.59, the refractive index of polystyrene is 1.59, the refractive index of polyamide (nylon) is 1.53, and the refractive index of polymethyl methacrylate is 1. 49, and the refractive index difference can be increased to about 0.5 by manufacturing the diffraction grating pigment as described above using these as resin materials. In the conventional diffraction grating pigment, this refractive index difference is about 0.1 to 0.2, and from the optical theory, the reflection intensity of the diffraction grating pigment of the present invention is more than five times that of the conventional diffraction grating pigment. be able to.
本発明の回折格子顔料は、例えば以下のようにして製造することができる。
まず、第一の樹脂を用いて、最終的な回折格子顔料中の中空部の形状に相当する凹凸形状の面を有する成形体を形成する。この成形体は一般的な樹脂の成形方、例えば押し出し、射出、型押し等によって形成する。第一の樹脂は、以下に説明するように後に除去されるが、その除去方法に応じて選択し、例えば溶解させて除去する場合には、用いる溶液もしくは溶媒に可溶である樹脂を用いる。すなわち、アルカリ水溶液により溶解除去する場合には、ポリ乳酸を用いることが好ましい。
The diffraction grating pigment of the present invention can be produced, for example, as follows.
First, a molded body having an uneven surface corresponding to the shape of the hollow portion in the final diffraction grating pigment is formed using the first resin. This molded body is formed by a general resin molding method, for example, extrusion, injection, embossing, or the like. The first resin is removed later, as will be described below. The first resin is selected according to the removal method. For example, when it is dissolved and removed, a resin that is soluble in the solution or solvent to be used is used. That is, polylactic acid is preferably used when dissolved and removed with an alkaline aqueous solution.
このポリ乳酸としては、Ｌ−乳酸を主成分とするものが一般的であるが、４０wt％を超えない範囲内でＤ−乳酸をはじめとする他の共重合成分を含有していてもよい。また、ポリエチレングリコールを共重合したポリエチレンテレフタレート又はポリブチレンテレフタレートは、ポリエチレングリコールの共重合割合が３０wt％以上となるようにすることが好ましく、このようにすることによりアルカリ溶解速度が著しく向上する。さらに、アルキルスルホン酸アルカリ金属塩及び／又はポリエチレングリコールを配合したポリエチレンテレフタレート及びポリブチレンテレフタレートは、前者は０．５〜３．０wt％の範囲、後者は１．０〜４．０wt％の範囲が好ましく、後者のポリエチレングリコールの平均分子量は６００〜４０００の範囲が適当である。 The polylactic acid is generally composed mainly of L-lactic acid, but may contain other copolymer components such as D-lactic acid within a range not exceeding 40 wt%. Further, polyethylene terephthalate or polybutylene terephthalate copolymerized with polyethylene glycol is preferably such that the copolymerization ratio of polyethylene glycol is 30 wt% or more, and by doing so, the alkali dissolution rate is remarkably improved. Further, polyethylene terephthalate and polybutylene terephthalate blended with alkali metal alkyl sulfonate and / or polyethylene glycol have a former range of 0.5 to 3.0 wt% and the latter range of 1.0 to 4.0 wt%. The average molecular weight of the latter polyethylene glycol is preferably in the range of 600 to 4000.
こうして第一の樹脂により成形体を形成後、第二の樹脂によりこの性形態を完全に被覆する。第二の樹脂は上記の粒子を形成する樹脂を用いる。こうして形成した複合体を用い、例えば溶融紡糸法により糸状物を形成する。次いでこの糸状物から第一の樹脂を除去する。この第一の樹脂の除去は、この第一の樹脂により形成された中空部の形状を損なうことがないよう、好ましくは適当な溶液もしくは溶剤に溶解させることにより行う。例えば、第一の樹脂として上記のポリ乳酸を用いた場合、糸状物をアルカリ水溶液、例えばアルカリ金属の水酸化物であるＫＯＨ，ＮａＯＨ等の２〜１０％水溶液に浸漬させ、さらに室温〜９０℃の温度にて加熱処理を行うことにより、ポリ乳酸を溶解させて除去することができる。 After forming a molded body with the first resin in this way, the second form of the resin is completely covered with this sex form. As the second resin, a resin that forms the above particles is used. Using the composite thus formed, a filamentous material is formed by, for example, a melt spinning method. Next, the first resin is removed from the filamentous material. The removal of the first resin is preferably performed by dissolving it in an appropriate solution or solvent so as not to impair the shape of the hollow portion formed by the first resin. For example, when the above polylactic acid is used as the first resin, the filamentous material is immersed in an aqueous alkali solution, for example, a 2-10% aqueous solution of KOH, NaOH or the like, which is an alkali metal hydroxide, and further room temperature to 90 ° C. The polylactic acid can be dissolved and removed by performing the heat treatment at the temperature.
こうして内部が中空となった糸状物を、例えばレーザーカットにより所定の厚み、具体的には１０〜１００μｍ、好ましくは２０μｍで切断し、切断面を融着によって封止することにより、本発明の回折格子顔料が得られる。 The filamentous material thus hollowed out is cut to a predetermined thickness, for example, 10 to 100 μm, preferably 20 μm, for example, by laser cutting, and the cut surface is sealed by fusion, whereby the diffraction of the present invention is performed. A lattice pigment is obtained.
本発明の回折格子顔料は、従来から顔料を利用してきた各種用途において、特に表面処理など施すことなくそのまま使用することができる。しかし、強酸性／強アルカリ性の溶液を利用する用途においては、耐薬品性をさらに向上させるため、透明な光輝性を製品に付与するというこの発明の目的を阻害しない範囲で、シリカ（ＳｉＯ２）やアルミニウムなどからなる保護膜を設けてもよい。同様に、耐水性や樹脂との混練性を高めるためにカップリング剤で表面処理してもよく、耐光性を向上させるために紫外線吸収被膜を成形してもよい。 The diffraction grating pigment of the present invention can be used as it is without any surface treatment in various applications where pigments have been conventionally used. However, in applications using strong acid / strong alkali solutions, silica (SiO 2 ) is used as long as it does not impair the object of the present invention to impart transparent glitter to a product in order to further improve chemical resistance. A protective film made of aluminum or aluminum may be provided. Similarly, surface treatment may be performed with a coupling agent in order to improve water resistance and kneadability with a resin, and an ultraviolet absorbing film may be formed in order to improve light resistance.
本発明の回折格子顔料は、ビヒクルや樹脂中に適量配合され、また他の着色顔料と併用されて、塗料、樹脂組成物等の各種用途に利用される。例えば、塗料組成物に含まれるビヒクルは、本発明の回折格子顔料を分散するものであって、塗膜形成用樹脂と必要に応じて架橋剤とから構成される。上記ビヒクルを構成する上記塗膜形成用樹脂としては、例えば、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、フッ素樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエーテル樹脂等が挙げられ、これらは、２種以上を組合わせて使用することができる。特に、アクリル樹脂及びポリエステル樹脂が好ましく用いられる。 The diffraction grating pigment of the present invention is blended in an appropriate amount in a vehicle or a resin and used in combination with other colored pigments for various uses such as paints and resin compositions. For example, the vehicle contained in the coating composition is for dispersing the diffraction grating pigment of the present invention, and is composed of a coating film forming resin and, if necessary, a crosslinking agent. Examples of the coating film forming resin constituting the vehicle include acrylic resins, polyester resins, alkyd resins, fluororesins, epoxy resins, polyurethane resins, polyether resins, and the like. Can be used together. In particular, an acrylic resin and a polyester resin are preferably used.
上記アクリル樹脂としては、アクリル系モノマーと他のエチレン性不飽和モノマーとの共重合体を挙げることができる。上記共重合に使用し得るアクリル系モノマーとしては、アクリル酸又はメタクリル酸のメチル、エチル、プロピル、ｎ−ブチル、ｉ−ブチル、ｔ−ブチル、２−エチルヘキシル、ラウリル、フェニル、ベンジル、２−ヒドロキシエチル、２−ヒドロキシプロピル等のエステル化物類、アクリル酸又はメタクリル酸２−ヒドロキシエチルのカプロラクトンの開環付加物類、アクリル酸グリシジル、メタクリル酸グリシジル、アクリルアミド、メタクリルアミド及びＮ−メチロールアクリルアミド、多価アルコールの（メタ）アクリル酸エステルなどがある。これらと共重合可能な上記他のエチレン性不飽和モノマーとしては、スチレン、α−メチルスチレン、イタコン酸、マレイン酸、酢酸ビニル等がある。 Examples of the acrylic resin include a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Examples of acrylic monomers that can be used for the copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxy of acrylic acid or methacrylic acid. Esterified compounds such as ethyl and 2-hydroxypropyl, ring-opening adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide and N-methylol acrylamide, polyvalent Examples include (meth) acrylic acid esters of alcohol. Examples of the other ethylenically unsaturated monomers copolymerizable with these include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.
上記ポリエステル樹脂としては、飽和ポリエステル樹脂や不飽和ポリエステル樹脂等が挙げられ、例えば、多塩基酸と多価アルコールを加熱縮合して得られた縮合物が挙げられる。多塩基酸としては、飽和多塩基酸、不飽和多塩基酸が挙げられ、飽和多塩基酸としては、例えば、無水フタル酸、テレフタル酸、コハク酸等が挙げられ、不飽和多塩基酸としては、例えば、マレイン酸、無水マレイン酸、フマル酸等が挙げられる。多価アルコールとしては、例えば、二価アルコール、三価アルコール等が挙げられ、二価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール等が挙げられ、三価アルコールとしては、例えば、グリセリン、トリメチロールプロパン等が挙げられる。 Examples of the polyester resin include saturated polyester resins and unsaturated polyester resins, and examples thereof include condensates obtained by heat condensation of a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include saturated polybasic acid and unsaturated polybasic acid. Examples of the saturated polybasic acid include phthalic anhydride, terephthalic acid, succinic acid, and the like. Examples thereof include maleic acid, maleic anhydride, and fumaric acid. Examples of the polyhydric alcohol include dihydric alcohol and trihydric alcohol. Examples of the dihydric alcohol include ethylene glycol and diethylene glycol. Examples of the trihydric alcohol include glycerin and trimethylolpropane. Etc.
また、上記塗膜形成用樹脂には、硬化性を有するタイプとラッカータイプがあるが、通常硬化性を有するタイプのものが使用される。硬化性を有するタイプの場合には、アミノ樹脂、（ブロック）ポリイソシアネート化合物、アミン系、ポリアミド系、多価カルボン酸等の架橋剤と混合して用いられ、加熱または常温で硬化反応を進行させることができる。また、硬化性を有しないラッカータイプの塗膜形成用樹脂と硬化性を有するタイプとを併用することも可能である。 In addition, the coating film forming resin includes a curable type and a lacquer type, and a normal curable type is used. In the case of a curable type, it is used by mixing with a crosslinking agent such as an amino resin, a (block) polyisocyanate compound, an amine, a polyamide, or a polyvalent carboxylic acid, and the curing reaction proceeds with heating or at room temperature. be able to. It is also possible to use a lacquer type coating film-forming resin having no curability and a curability type in combination.
上記ビヒクルが架橋剤を含む場合、塗膜形成用樹脂と架橋剤との割合としては、固形分換算で塗膜形成用樹脂が９０〜５０wt％、架橋剤が１０〜５０wt％であり、好ましくは塗膜形成用樹脂が８５〜６０wt％であり、架橋剤が１５〜４０wt％である。架橋剤が１０wt％未満では（塗膜形成用樹脂が９０wt％を超えると）、塗膜中の架橋が十分でない。一方、架橋剤が５０wt％を超えると（塗膜形成用樹脂が５０wt％未満では）、光輝性塗料組成物の貯蔵安定性が低下するとともに硬化速度が大きくなるため、塗膜外観が悪くなる。 When the vehicle contains a cross-linking agent, the ratio of the resin for forming a coating film and the cross-linking agent is 90-50 wt% for the resin for forming the coating film and 10-50 wt% for the cross-linking agent in terms of solid content, preferably The film-forming resin is 85 to 60 wt%, and the crosslinking agent is 15 to 40 wt%. When the crosslinking agent is less than 10 wt% (when the coating film forming resin exceeds 90 wt%), crosslinking in the coating film is not sufficient. On the other hand, if the crosslinking agent exceeds 50 wt% (if the coating film forming resin is less than 50 wt%), the storage stability of the glittering coating composition is lowered and the curing rate is increased, so that the coating film appearance is deteriorated.
本発明の回折格子顔料を含む塗料組成物においては、着色顔料を含有することもできる。このようなものとして、従来から塗料用として常用されているものが用いられる。有機顔料としては、例えば、アゾレーキ系顔料、フタロシアニン系顔料、インジゴ系顔料、ペリレン系顔料、キノフタロン系顔料、ジオキサジン系顔料、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、また、無機顔料としては、例えば、黄鉛、黄色酸化鉄、ベンガラ、二酸化チタン、カーボンブラック等が挙げられる。光輝性顔料および／または着色顔料を含む場合の添加量は、得られる塗膜の透明性を損なわない範囲の量を含有することができる。また各種体質顔料を併用することができる。 The coating composition containing the diffraction grating pigment of the present invention may contain a coloring pigment. As such a thing, what is conventionally used conventionally for paints is used. Examples of organic pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, and the like. Examples of the inorganic pigment include chrome lead, yellow iron oxide, bengara, titanium dioxide, and carbon black. The addition amount in the case of containing a luster pigment and / or a color pigment can contain an amount in a range that does not impair the transparency of the resulting coating film. Various extender pigments can be used in combination.
本発明の回折格子顔料を含む塗料組成物は、上記成分の他に、脂肪族アミドの潤滑分散体であるポリアミドワックスや酸化ポリエチレンを主体としたコロイド状分散体であるポリエチレンワックス、沈降防止剤、硬化触媒、紫外線吸収剤、酸化防止剤、レベリング剤、シリコーンや有機高分子等の表面調整剤、タレ止め剤、増粘剤、消泡剤、架橋性重合体粒子（ミクロゲル）等を適宜含有することができる。これらの添加剤は、通常、上記ビヒクル１００質量部（固形分基準）に対して、例えば、それぞれ１５質量部以下の割合で配合することにより、塗料や塗膜の性能を改善することができる。 In addition to the above components, the coating composition containing the diffraction grating pigment of the present invention includes a polyamide wax which is a lubricating dispersion of an aliphatic amide, a polyethylene wax which is a colloidal dispersion mainly composed of oxidized polyethylene, an anti-settling agent, Contains a curing catalyst, ultraviolet absorber, antioxidant, leveling agent, surface conditioner such as silicone and organic polymer, sagging inhibitor, thickener, antifoaming agent, crosslinkable polymer particles (microgel), etc. be able to. These additives can usually improve the performance of the paint or coating film by blending, for example, at a ratio of 15 parts by mass or less with respect to 100 parts by mass (based on solid content) of the vehicle.
本発明の回折格子顔料を含む塗料組成物は、上記構成成分を、通常、溶剤に溶解または分散した態様で提供される。溶剤としては、ビヒクルを溶解または分散するものであればよく、有機溶剤および／または水を使用し得る。有機溶剤としては、塗料用として常用されているものを挙げることができる。例えば、トルエン、キシレン等の炭化水素類、アセトン、メチルエチルケトン等のケトン類、酢酸エチル、セロソルブアセテート、ブチルセロソルブ等のエステル類、アルコール類等を例示できる。環境面の観点から有機溶剤の使用が規制されている場合には、水を用いることが好ましい。この場合、適量の親水性有機溶剤を含有させてもよい。 The coating composition containing the diffraction grating pigment of the present invention is provided in a form in which the above-mentioned constituents are usually dissolved or dispersed in a solvent. Any solvent can be used as long as it dissolves or disperses the vehicle, and an organic solvent and / or water can be used. Examples of the organic solvent include those commonly used for paints. Examples thereof include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate and butyl cellosolve, alcohols and the like. Water is preferably used when the use of organic solvents is restricted from an environmental point of view. In this case, an appropriate amount of a hydrophilic organic solvent may be contained.
本発明の回折格子顔料を含む塗膜層は、溶剤型塗料または粉体型塗料により形成してもよい。溶剤型塗料としては、一液型塗料を用いてもよいし、二液型ウレタン樹脂塗料等のような二液型塗料を用いてもよい。塗膜平滑性の点からは、溶剤型塗料が好ましい。 The coating layer containing the diffraction grating pigment of the present invention may be formed of a solvent-type paint or a powder-type paint. As the solvent-type paint, a one-part paint may be used, or a two-part paint such as a two-part urethane resin paint may be used. From the viewpoint of coating film smoothness, a solvent-type paint is preferred.
本発明の回折格子顔料を含む塗膜層の乾燥膜厚は、１０〜１００μｍが好ましく、１０μｍ未満では回折格子顔料による光輝感が、十分に発現できず、１００μｍを超えると塗膜外観が、不充分となる恐れがある。より好ましくは２０〜５０μｍである。 The dry film thickness of the coating layer containing the diffraction grating pigment of the present invention is preferably 10 to 100 μm, and if it is less than 10 μm, the glitter feeling due to the diffraction grating pigment cannot be sufficiently exhibited. There is a risk that it will be sufficient. More preferably, it is 20-50 micrometers.
本発明の回折格子顔料を含む塗膜形成方法における好ましい態様は、回折格子顔料含有クリヤー塗膜層が、回折格子顔料含有クリヤー塗膜と回折格子顔料を含んでいないクリヤー塗膜とからなる２層構造からなるものであり、この２層の塗膜が、ウェットオンウェットの２コート１ベークで形成されることが好ましい。この２層構造からなる場合には、光輝感及び塗膜外観を一層向上させることができるため、平滑性の高い、深み感のある光輝性塗膜を得ることができる。この場合の回折格子顔料含有光輝性クリヤー塗膜の膜厚は、上記回折格子顔料を含む塗膜層を一層で形成する場合と同じであり、クリヤー塗膜は、２０〜１００μｍが好ましく、この範囲を外れると塗膜外観が不十分となる恐れがある。 In a preferred embodiment of the method for forming a coating film containing a diffraction grating pigment of the present invention, the clear coating layer containing a diffraction grating pigment comprises two layers comprising a clear coating film containing a diffraction grating pigment and a clear coating film containing no diffraction grating pigment. The two-layer coating film is preferably formed by wet-on-wet two-coat one-bake. In the case of the two-layer structure, the glitter feeling and the appearance of the coating film can be further improved, so that a glitter coating film having a high smoothness and a deep feeling can be obtained. In this case, the film thickness of the brilliant clear coating film containing the diffraction grating pigment is the same as that when the coating film layer containing the diffraction grating pigment is formed in a single layer, and the clear coating film is preferably 20 to 100 μm, and this range. Otherwise, the appearance of the coating film may be insufficient.
塗料中における回折格子顔料の含有率は、乾燥硬化後の塗膜において０．１〜３０wt％となるように調整することが好ましい。より好ましい含有率は、１〜２０wt％である。回折格子顔料の含有率が０．１wt％よりも少ない場合は、塗膜に十分な虹色の発現がなく、一方３０wt％よりも多いと、含有率の割には光輝性の向上が小さくなり、却って素地の色調を損なってしまうおそれが生じる。この回折格子顔料は、素地の色調を損なうことがないので、各色の塗料に利用することができる。 The content of the diffraction grating pigment in the paint is preferably adjusted so that it is 0.1 to 30 wt% in the coating film after drying and curing. A more preferable content rate is 1 to 20 wt%. When the content of the diffraction grating pigment is less than 0.1 wt%, the coating film does not exhibit a sufficient rainbow color. On the other hand, when the content is more than 30 wt%, the improvement in glitter is small for the content. On the contrary, there is a risk that the color tone of the substrate may be impaired. Since this diffraction grating pigment does not impair the color tone of the substrate, it can be used for paints of various colors.
本発明の回折格子顔料を樹脂組成物中に配合する場合は、母材樹脂に上記の各種熱硬化性樹脂または熱可塑性樹脂を利用することができる。特に、熱可塑性樹脂に使用すれば、射出成形が可能となるため、複雑な形状の成型品を得ることができる。 When the diffraction grating pigment of the present invention is blended in the resin composition, the above-mentioned various thermosetting resins or thermoplastic resins can be used as the base resin. In particular, if it is used for a thermoplastic resin, injection molding becomes possible, so that a molded product having a complicated shape can be obtained.
本発明の回折格子顔料はインキ組成物にも用いることができる。インキ組成物には、各種ボールペン、フェルトペンなどの筆記具用インキ並びにグラビアインキ、オフセットインキなどの印刷インキがあるが、いずれのインキ組成物にも使用することができる。筆記具用インキのビヒクルの例としては、アクリル樹脂、スチレン−アクリル共重合体、ポリビニルアルコール、ポリアクリル酸塩、アクリル酢酸ビニル共重合体、ザンサンガムなどの微生物産性多糖類またはグアーガムなどの水溶性植物性多糖類などと、溶剤としての水、アルコール、炭化水素、エステルなどからなるものとが挙げられる。 The diffraction grating pigment of the present invention can also be used in an ink composition. Ink compositions include inks for writing instruments such as various ballpoint pens and felt pens, and printing inks such as gravure inks and offset inks, and can be used in any ink composition. Examples of inks for writing instruments include acrylic resins, styrene-acrylic copolymers, polyvinyl alcohol, polyacrylic acid salts, vinyl acrylate copolymers, water-soluble plants such as microbial polysaccharides such as xanthan gum or guar gum And the like, and those composed of water, alcohol, hydrocarbon, ester and the like as a solvent.
グラビアインキ用ビヒクルの例としては、ガムロジン、ウッドロジン、トール油ロジン、ライムロジン、ロジンエスエル、マレイン酸樹脂、ポリアミド樹脂、ビニル樹脂、ニトロセルロース、酢酸セルロース、エチルセルロース、塩化ゴム、環化ゴム、エチレン−酢酸ビニル共重合樹脂、ウレタン樹脂、ポリエステル樹脂、アルキド樹脂、ギルソナイト、ダンマル若しくはセラックなどの樹脂混合物、上記樹脂の混合物、上記樹脂を水溶化した水溶性樹脂又は水性エマルション樹脂と、炭化水素、アルコール、エーテル、エステル又は水などの溶剤とからなるものが挙げられる。 Examples of gravure ink vehicles include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin shell, maleic resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate, ethyl cellulose, chlorinated rubber, cyclized rubber, ethylene-acetic acid Resin mixture such as vinyl copolymer resin, urethane resin, polyester resin, alkyd resin, gilsonite, dammar or shellac, mixture of the above resin, water-soluble resin or aqueous emulsion resin in which the above resin is water-solubilized, and hydrocarbon, alcohol, ether , Esters and water and other solvents.
オフセットインキ用ビヒクルの例としては、ロジン変性フェノール樹脂、石油樹脂、アルキド樹脂またはこれらの乾性変性樹脂などの樹脂と、アマニ油、桐油または大豆油などの植物油と、ｎ−パラフィン、イソパラフィン、アロマテック、ナフテン、α−オレフィンまたは水などの溶剤とからなるものが挙げられる。なお、上記の各種ビヒクル成分には、染料、顔料、各種界面活性剤、潤滑剤、消泡剤、レベリング剤などの慣用の添加剤を適宜選択して配合してもよい。 Examples of vehicles for offset ink include rosin-modified phenolic resins, petroleum resins, alkyd resins, or resins such as these dry-modified resins, vegetable oils such as linseed oil, tung oil or soybean oil, and n-paraffin, isoparaffin, aromatech. , Naphthene, α-olefin, or a solvent such as water. It should be noted that conventional additives such as dyes, pigments, various surfactants, lubricants, antifoaming agents, and leveling agents may be appropriately selected and blended with the various vehicle components.
実施例１
第一の樹脂としてポリ乳酸を、第二の樹脂としてポリメチルメタクリレート（屈折率：ｎ＝１．４８）を用い、溶融紡糸により糸状物を成形後、アルカリ溶液（４％ＮａＯＨ水溶液）に浸漬して８０℃に加熱し、ポリ乳酸を溶解させ、回折格子部を空洞化させ、これをレーザーカットして図１に示すような回折格子顔料を製造した。この顔料のサイズは、厚み２μｍ、長径２０μｍ、短径１μｍであり、凸部の頂点間距離は２μｍであった。
Example 1
Polylactic acid is used as the first resin and polymethyl methacrylate (refractive index: n = 1.48) is used as the second resin. After forming a filament by melt spinning, it is immersed in an alkaline solution (4% NaOH aqueous solution). The mixture was heated to 80 ° C. to dissolve the polylactic acid, the diffraction grating portion was hollowed, and this was laser cut to produce a diffraction grating pigment as shown in FIG. The pigment had a thickness of 2 μm, a major axis of 20 μm and a minor axis of 1 μm, and the distance between the vertices of the convex portions was 2 μm.
この回折格子顔料をアクリルメラミン塗料にＰＷＣ（顔料質量比）１０％で混合してベース塗料とした。黒中塗りを塗装した鋼板に、上述のベース塗料を約１５μｍ塗装し、焼付せずにアクリルメラミン系のクリヤー塗料を約３０μｍ塗装し、１４０℃で３０分間焼付けた。製造された顔料は、分光された虹色を発色し、優れた意匠効果を有することを確認した。 This diffraction grating pigment was mixed with acrylic melamine paint at a PWC (pigment mass ratio) of 10% to obtain a base paint. About 15 μm of the above-mentioned base coating was applied to the steel plate coated with black intermediate coating, and an acrylic melamine-based clear coating was applied about 30 μm without baking, and baked at 140 ° C. for 30 minutes. It was confirmed that the produced pigment developed a spectroscopic rainbow color and had an excellent design effect.
実施例２
第一の樹脂としてポリ乳酸を、第二の樹脂としてポリエチレンテレフタレート（屈折率：ｎ＝１．５８）を用い、溶融紡糸により糸状物を成形後、アルカリ溶液（４％ＮａＯＨ水溶液）に浸漬して６０℃に加熱し、ポリ乳酸を溶解させ、回折格子部を空洞化させ、これをレーザーカットして図１に示すような回折格子顔料を製造した。この顔料のサイズは、厚み２μｍ、長径２０μｍ、短径１μｍであり、凸部の頂点間距離は２μｍであった。実施例１と同様の方法で塗膜を作製したところ、製造された顔料は、分光された虹色を発色し、優れた意匠効果を有することを確認した。
Example 2
Polylactic acid is used as the first resin and polyethylene terephthalate (refractive index: n = 1.58) is used as the second resin. By heating to 60 ° C., polylactic acid was dissolved, the diffraction grating portion was hollowed, and this was laser-cut to produce a diffraction grating pigment as shown in FIG. The pigment had a thickness of 2 μm, a major axis of 20 μm and a minor axis of 1 μm, and the distance between the vertices of the convex portions was 2 μm. When a coating film was produced in the same manner as in Example 1, it was confirmed that the produced pigment developed a spectral rainbow color and had an excellent design effect.
比較例１
第一の樹脂としてポリエチレンテレフタレート（屈折率：ｎ＝１．５８）を、第二の樹脂としてポリメチルメタクリレート（屈折率：ｎ＝１．４８）を用い、溶融紡糸により糸状物を成形後、これをレーザーカットして、中空部に対応する部位に第一の樹脂が配置されている回折格子顔料を製造した。この顔料のサイズは、厚み２μｍ、長径２０μｍ、短径１μｍであり、凸部の頂点間距離は２μｍであった。実施例１と同様の方法で塗膜を作製したところ、製造された顔料は、分光された虹色を発色しなかった。これは、回折格子部の屈折率差が０．１と小さすぎるためであると考えられる。
Comparative Example 1
Polyethylene terephthalate (refractive index: n = 1.58) is used as the first resin, polymethyl methacrylate (refractive index: n = 1.48) is used as the second resin, and a filamentous material is formed by melt spinning. Was cut to produce a diffraction grating pigment in which the first resin was disposed in a portion corresponding to the hollow portion. The pigment had a thickness of 2 μm, a major axis of 20 μm and a minor axis of 1 μm, and the distance between the vertices of the convex portions was 2 μm. When a coating film was produced in the same manner as in Example 1, the produced pigment did not develop a spectroscopic rainbow color. This is presumably because the difference in refractive index of the diffraction grating portion is as small as 0.1.
比較例２
第一の樹脂としてポリ乳酸を、第二の樹脂としてポリメチルメタクリレート（屈折率：ｎ＝１．４８）を用い、溶融紡糸により糸状物を成形後、アルカリ溶液（４％ＮａＯＨ水溶液）に浸漬して７０℃に加熱し、ポリ乳酸を溶解させ、回折格子部を空洞化させ、これを従来の剪断カット工法にて切断して回折格子顔料を製造した。この顔料のサイズは、厚み２μｍ、長径２０μｍ、短径１μｍであり、凸部の頂点間距離は２μｍであった。実施例１と同様の方法で塗膜を作製したところ、製造された顔料は分光された虹色を発色しなかった。これは、回折格子部の中空部が密閉されず、塗料樹脂がこの中空部を埋めてしまい、屈折率差がなくなってしまったためである。
Comparative Example 2
Polylactic acid is used as the first resin and polymethyl methacrylate (refractive index: n = 1.48) is used as the second resin. After forming a filament by melt spinning, it is immersed in an alkaline solution (4% NaOH aqueous solution). And heated to 70 ° C. to dissolve the polylactic acid to make the diffraction grating portion hollow, and this was cut by a conventional shear cut method to produce a diffraction grating pigment. The pigment had a thickness of 2 μm, a major axis of 20 μm and a minor axis of 1 μm, and the distance between the vertices of the convex portions was 2 μm. When a coating film was produced in the same manner as in Example 1, the produced pigment did not develop a spectral rainbow color. This is because the hollow portion of the diffraction grating portion is not sealed, and the coating resin fills the hollow portion, and the refractive index difference disappears.
１ 回折格子顔料 1 Diffraction grating pigment
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000246829A (en) * | 1999-02-26 | 2000-09-12 | Nissan Motor Co Ltd | Coloring structure |
| JP2003277690A (en) * | 2002-03-26 | 2003-10-02 | Dainippon Toryo Co Ltd | Method for surface-treatment of luster pigment for metallic powder coating material |
| JP2005008651A (en) * | 2003-06-16 | 2005-01-13 | Toyota Motor Corp | Diffraction grating pigment and method for producing the same, coating and resin composition |
| JP2005264123A (en) * | 2004-03-22 | 2005-09-29 | Toyota Motor Corp | Diffraction grating pigment and method for producing the same, coating and resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000246829A (en) * | 1999-02-26 | 2000-09-12 | Nissan Motor Co Ltd | Coloring structure |
| JP2003277690A (en) * | 2002-03-26 | 2003-10-02 | Dainippon Toryo Co Ltd | Method for surface-treatment of luster pigment for metallic powder coating material |
| JP2005008651A (en) * | 2003-06-16 | 2005-01-13 | Toyota Motor Corp | Diffraction grating pigment and method for producing the same, coating and resin composition |
| JP2005264123A (en) * | 2004-03-22 | 2005-09-29 | Toyota Motor Corp | Diffraction grating pigment and method for producing the same, coating and resin composition |
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