JP2011122036A - Resin composition exerting color flip-flop effect - Google Patents
Resin composition exerting color flip-flop effect Download PDFInfo
- Publication number
- JP2011122036A JP2011122036A JP2009280010A JP2009280010A JP2011122036A JP 2011122036 A JP2011122036 A JP 2011122036A JP 2009280010 A JP2009280010 A JP 2009280010A JP 2009280010 A JP2009280010 A JP 2009280010A JP 2011122036 A JP2011122036 A JP 2011122036A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- molded product
- inorganic pigment
- color
- fine particle
- 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
Images
Abstract
Description
本発明は、成形物にした時に、該成形物を見る者にカラーフリップフロップ効果を示す樹脂組成物に関する。 The present invention relates to a resin composition that exhibits a color flip-flop effect to a viewer of a molded product when the molded product is formed.
従来、車輛のメタリック塗装において、メタリック顔料を用いたメタリック塗料が使用されている。また、樹脂成形体分野においても受光角度差における明度差ΔＬをフリップフロップ効果として、これをメタリックの基準としている。従来のメタリック色では、明度差ΔＬが大きいが、色相差ΔａまたはΔｂは大きくない。 Conventionally, metallic paints using metallic pigments have been used in metallic coating of vehicles. Also in the field of resin moldings, the lightness difference ΔL in the light receiving angle difference is used as a flip-flop effect, which is used as a metallic reference. In the conventional metallic color, the lightness difference ΔL is large, but the hue difference Δa or Δb is not large.
従って本発明の目的は、成形物としたときに成形物表面を見る角度や照明の角度によって、明度差ΔＬ*が大きく、且つ色相差Δａ*またはΔｂ*も大きいカラーフリップフロップ効果を与える樹脂組成物を提供することである。 Accordingly, an object of the present invention is to provide a resin composition that gives a color flip-flop effect that has a large brightness difference ΔL * and a large hue difference Δa * or Δb * depending on the angle of viewing the surface of the molded product or the angle of illumination when the molded product is formed. Is to provide things.
上記目的は以下の本発明によって達成される。すなわち、本発明は、アスペクト比が３以上である無機顔料Ａと、一次粒子径の数平均値が１５０ｎｍ以下の無機顔料Ｂとを含有する樹脂組成物であって、成形物にした時の成形物表面に対する正反射に対する受光角が１１０°と１５°におけるΔａ*が１０より大きく、および／またはΔｂ*が１０より大きいカラーフリップフロップ効果を示すことを特徴とする樹脂組成物を提供する。 The above object is achieved by the present invention described below. That is, the present invention is a resin composition containing an inorganic pigment A having an aspect ratio of 3 or more and an inorganic pigment B having a number average value of primary particle diameters of 150 nm or less, and molded when formed into a molded product. Provided is a resin composition characterized by exhibiting a color flip-flop effect in which Δa * is greater than 10 and / or Δb * is greater than 10 at a light receiving angle of 110 ° and 15 ° with respect to regular reflection on an object surface.
上記本発明においては、無機顔料Ａが、アルミ粉および無機物でコートしたパール系顔料から選ばれる少なくとも１種であること；および無機顔料Ｂが、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化スズおよび微粒子酸化セリウムから選ばれる少なくとも１種であることが好ましい。 In the present invention, the inorganic pigment A is at least one selected from pearl pigments coated with aluminum powder and an inorganic substance; and the inorganic pigment B is fine particle titanium oxide, fine particle zinc oxide, fine particle tin oxide and fine particles. It is preferably at least one selected from cerium oxide.
本発明者は、鋭意検討の結果、樹脂にメタリック色顔料と、これに加えて特定の微粒子酸化物を添加することにより、該樹脂組成物からなる成形物の表面は、ΔＬ*だけではなくΔａ*やΔｂ*などの色相も変化するカラーフリップフロップ効果が発現することを見いだした。これにより、従来にない陰影のあるメタリック調意匠性樹脂成形物を得ることが可能となった。 As a result of intensive studies, the present inventors have added a metallic color pigment and a specific fine particle oxide to the resin, so that the surface of the molded product made of the resin composition is not only ΔL * but also Δa. It was found that a color flip-flop effect in which hues such as * and Δb * also change was developed. As a result, it has become possible to obtain a metallic design resin molded product having an unprecedented shade.
次に発明を実施するための形態を挙げて本発明をさらに詳しく説明する。本発明の樹脂組成物に使用する樹脂としては、例えば、ポリエチレン、ポリプロピレンなどのオレフィン系樹脂、ＰＶＣ系樹脂、フッ素系樹脂、ポリスチレン、ＡＳ、ＡＢＳなどのＰＳ系樹脂、エラストマー系樹脂、ＰＥＴ、ＰＢＴ、ＰＣなどのポリエステル系樹脂、ＰＡ６、ＰＡ６６などのポリアミド系樹脂、ＰＯＭ、ポリイミド系樹脂などの熱可塑性樹脂およびその混合物が有効である。 Next, the present invention will be described in more detail with reference to modes for carrying out the invention. Examples of the resin used in the resin composition of the present invention include olefin resins such as polyethylene and polypropylene, PVC resins, fluorine resins, PS resins such as polystyrene, AS, and ABS, elastomer resins, PET, and PBT. Polyester resins such as PC, polyamide resins such as PA6 and PA66, thermoplastic resins such as POM and polyimide resins, and mixtures thereof are effective.
本発明で使用する無機顔料Ａとしては、無機物でコートしたパール系顔料、すなわち、チタンコートマイカ、酸化鉄コートマイカ、無機物コートガラス、無機物コートアルミナや、パール系顔料、アルミ粉など、アスペクト比が３以上で、樹脂組成物にメタリック色を付与する意匠性顔料を使用する。無機顔料Ａの添加量は、樹脂に対して０．５質量％〜１０質量％の添加量が有効である。添加量が多いほど目標の色彩効果が出やすく、１質量％かそれを超えるとより出やすくなる。添加量の上限１０質量％は成形物に求められる強度で決る。本発明においては、チタンコートマイカかアルミ粉が特に色彩効果が高い。そして、その中でも特に色彩効果が高い上に成分・形状とも安定して供給されるため、チタンコートマイカでは、メルク製、商品名イリオジン１００〜１９９の何れかがよい。同じくアルミ粉では、東洋アルミ製、アルペースト各グレードが特に効果的である。なお、イリオジン１００〜１９９のアスペクト比は、１０〜１００の範囲内である。また、アルペースト各グレードのアスペクト比は、２０〜２００の範囲内である。 As the inorganic pigment A used in the present invention, the pearl pigment coated with an inorganic substance, that is, titanium coated mica, iron oxide coated mica, inorganic coated glass, inorganic coated alumina, pearl pigment, aluminum powder, etc. have an aspect ratio. A designable pigment that imparts a metallic color to the resin composition at 3 or more is used. As the addition amount of the inorganic pigment A, an addition amount of 0.5 to 10% by mass with respect to the resin is effective. The greater the amount added, the easier the target color effect will be, and the more likely it will be when 1% by mass or more. The upper limit of 10% by mass of the addition amount is determined by the strength required for the molded product. In the present invention, titanium coated mica or aluminum powder has a particularly high color effect. Among them, since the color effect is particularly high and the components and shapes are stably supplied, any of titanium-coated mica made by Merck and trade names Iriodin 100 to 199 is preferable. For aluminum powder, Toyo Aluminum and Alpaste grades are particularly effective. In addition, the aspect ratio of Iriodin 100-199 is in the range of 10-100. Moreover, the aspect ratio of each grade of Alpaste is in the range of 20-200.
本発明で使用する無機顔料Ｂとしては、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化スズおよび微粒子酸化セリウムなどである。特にこの４種の何れかが色彩効果に優れる。そしてこれらのものの一次粒子径の数平均値が１０〜１５０ｎｍの微粒子の市販各種のものが有効である。特に好ましくは、一次粒子径の数平均値が１０〜６０ｎｍのさらに細かい物が、色彩効果が高く特に良い。微粒子酸化チタンとしてテイカ製、ＭＴ７００ＨＤ、微粒子酸化亜鉛としてハクスイテック製、ジンクオックススーパーＦ−３が、成分・形状とも安定して供給される例として挙げられる。それらの添加量としては樹脂に対して０．２質量％〜５質量％が有効である。添加量が多いほど目標の色彩効果が出やすく、添加量の上限は成形物に求められる強度で決る。 Examples of the inorganic pigment B used in the present invention include fine particle titanium oxide, fine particle zinc oxide, fine particle tin oxide, and fine particle cerium oxide. In particular, any of these four types is excellent in color effect. Various commercially available fine particles having a primary average particle diameter of 10 to 150 nm are effective. Particularly preferably, finer particles having a primary particle diameter number average value of 10 to 60 nm are particularly good because of high color effect. As examples of finely divided titanium oxide manufactured by Teika, MT700HD, fine particle zinc oxide manufactured by Hakusui Tech Co., Ltd., Zinc Ox Super F-3 can be stably supplied in both components and shape. An effective addition amount thereof is 0.2% by mass to 5% by mass with respect to the resin. The larger the amount added, the easier the target color effect will be, and the upper limit of the amount added is determined by the strength required of the molded product.
無機顔料Ａ／無機顔料Ｂの割合（質量）は、１０／１〜２／１の範囲で目標の色彩効果が出やすい。なおカラーフリップフロップ性は、市販の変角スペクトロフォトメーター（分光光度計）にて測定し、車輛のメタリック塗装において、ある程度普及している「５変角評価」の角度の小さい方のハイライトと、角度の大きい方のシェードの評価、すなわち、正反射に対する受光角１５°と１１０°の分光反射率を測定し、各々のＣＩＥのＬ*ａ*ｂ*３つの値の差により評価すればよい。すなわち、Ｌ*値だけでなく、ａ*値かｂ*値の少なくとも一方の角度差が大きければ、色相の角度変化の大きなフリップフロップが出ていることになる。通常ａ*ｂ*の少なくともどちらかの差が、少なくとも６に達すると、目視でも大きく色は異なって見える。そして、受光角１５°と１１０°との差で１０より大きくなれば、５変角評価の差の小さい方の受光角、受光角２５°対７５°でも同様に６に達するのはほぼ確実なので、受光角１５°と１１０°との差で、上記の差（１０）が出ていることが最低限の目標となる。更に受光角１５°と１１０°との差が２０より大きくなると、受光角２５°対７５°でも「非常に大きい色差」とされる差が１２に達するのはほぼ確実なので、なおさら良いと言える。なお受光角１５°と１１０°との差で評価する方法は、その他の角度の組合せに比べて、本発明の条件では、色差の絶対値が大きくなるため測定精度が増し、本発明品の品質を安定させるという点で、より好ましい測定手法である。 The ratio (mass) of inorganic pigment A / inorganic pigment B is easily in the range of 10/1 to 2/1, and the target color effect is likely to appear. The color flip-flop is measured with a commercially available variable angle spectrophotometer (spectrophotometer), and the highlight of the smaller angle of “5 angle change evaluation”, which is widely used in metallic coating of vehicles, Evaluation of the shade having the larger angle, that is, the spectral reflectance at the light receiving angles of 15 ° and 110 ° with respect to the regular reflection is measured and evaluated by the difference between the three values of L * a * b * of each CIE. . That is, if not only the L * value but also the angle difference of at least one of the a * value or the b * value is large, a flip-flop having a large hue angle change is output. Usually, when at least one of the differences in a * b * reaches at least 6, the color appears greatly different visually. If the difference between the light receiving angles of 15 ° and 110 ° is greater than 10, it is almost certain that 6 will be reached in the same way even at the light receiving angle with the smaller difference in the 5 variable angle evaluation, the light receiving angle of 25 ° to 75 °. The minimum target is that the difference (10) is the difference between the light receiving angles of 15 ° and 110 °. Furthermore, when the difference between the light receiving angles of 15 ° and 110 ° is larger than 20, it is almost certain that the difference of “very large color difference” reaches 12 even when the light receiving angle is 25 ° to 75 °, and is even better. Note that the evaluation method based on the difference between the light receiving angles of 15 ° and 110 ° increases the measurement accuracy because the absolute value of the color difference increases under the conditions of the present invention compared to other angle combinations. This is a more preferable measurement method in that it is stable.
本発明の樹脂組成物は、前記の樹脂と無機顔料Ａと無機顔料Ｂとを混合し、任意の混練機、例えば、押出機などで混練し、ペレット状、フレーク状、粉状の組成物として得られる。マスターバッチなど、顔料成分の濃度の高い物を中間に作成し、通常の通り、それを更に薄めて使ってもよい。 The resin composition of the present invention is a mixture of the resin, the inorganic pigment A, and the inorganic pigment B, kneaded with an arbitrary kneader, for example, an extruder, etc., as a pellet-like, flake-like, or powder-like composition. can get. A product having a high concentration of pigment component such as a masterbatch may be prepared in the middle and further diluted as usual.
なお、必要に応じて本発明の樹脂組成物には、顔料分散剤、紫外線吸収剤、光安定剤、酸化防止剤、難燃剤、帯電防止剤、スリップ剤、無機フィラーなど、メタリック発色を阻害しない範囲で各種添加剤の添加が可能である。 If necessary, the resin composition of the present invention does not inhibit metallic color development such as pigment dispersant, ultraviolet absorber, light stabilizer, antioxidant, flame retardant, antistatic agent, slip agent, inorganic filler, etc. Various additives can be added within the range.
また、本発明の樹脂組成物の成形法として、射出成形、パイプ成形、ブロー成形、インフレーション成形、Ｔダイ成形など任意の成形法に使用可能である。このような成形方法で成形した成形物の表面のうち少なくとも一部を、平らな面（鏡面）にすると、（成形物表面に対する正反射に対する受光角が１１０°と１５°における）明度差ΔＬ*が大きいだけでなく、色相差にあたる、Δａ*が１０より大きく、および／またはΔｂ*が１０より大きい、優れたカラーフリップフロップ効果を有する成形物が、前記樹脂組成物より得られる。 Moreover, as a molding method of the resin composition of the present invention, it can be used for any molding method such as injection molding, pipe molding, blow molding, inflation molding, T-die molding. When at least a part of the surface of the molded product molded by such a molding method is a flat surface (mirror surface), the lightness difference ΔL * (when the light receiving angles with respect to the regular reflection with respect to the molded product surface are 110 ° and 15 °) . A molded product having an excellent color flip-flop effect, in which Δa * is greater than 10 and / or Δb * is greater than 10, which corresponds to a hue difference, is obtained from the resin composition.
次に実施例および比較例を挙げて本発明をさらに具体的に説明する。なお、文中の「％」は特に断りのない限り質量基準である。
［実施例１］
ポリプロピレン樹脂（プライムポリマーＪ１０４）に、パール系顔料としてチタンコートマイカ（メルク製、イリオジン１２０）を１．０％、および微粒子酸化亜鉛（ハクスイテック製、ジンクオックススーパーＦ−３：数平均一次粒子径５０ｎｍ）を０．２％添加し、ブレンドした混合物を４０ｍｍφ単軸押出機にて混練・ペレタイズして着色樹脂ペレットを作成した。このペレットを型締め５０ｔの射出成形機にて成形板（９０ｍｍ×５０ｍｍ×２．５ｍｍ）を成形して、成形物表面のカラーフリップフロップ性を測定した。
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “%” is based on mass unless otherwise specified.
[Example 1]
Polypropylene resin (Prime polymer J104), 1.0% titanium coated mica (Merck, Iriodin 120) as a pearl pigment, and fine zinc oxide (Haxitek, Zinc Ox Super F-3: number average primary particle size 50 nm 0.2%) was added, and the blended mixture was kneaded and pelletized with a 40 mmφ single screw extruder to prepare colored resin pellets. This pellet was molded into a molding plate (90 mm × 50 mm × 2.5 mm) with an injection molding machine having a mold clamping of 50 t, and the color flip-flop property on the surface of the molded product was measured.
［実施例２］
ポリメチルメタクリレート樹脂（スミペックスＬＧ）にアルミ粉（東洋アルミ製、アルペーストＦ Ｍ１４１５）を１．０％、および微粒子酸化チタン（テイカ製、ＭＴ７００ＨＤ：数平均一次粒子径５０ｎｍ）を０．２％添加し、ブレンドした混合物を４０ｍｍφ単軸押出機にて混練・ペレタイズして着色樹脂ペレットを作成した。このペレットを型締め５０ｔの射出成形機にて成形板（９０ｍｍ×５０ｍｍ×２．５ｍｍ）を成形して、成形物表面のカラーフリップフロップ性を測定した。
[Example 2]
Add 1.0% aluminum powder (Toyo Aluminum, Alpaste FM1415) and 0.2% fine particle titanium oxide (Taika, MT700HD: number average primary particle size 50 nm) to polymethyl methacrylate resin (Sumipex LG) The blended mixture was kneaded and pelletized with a 40 mmφ single screw extruder to prepare colored resin pellets. This pellet was molded into a molding plate (90 mm × 50 mm × 2.5 mm) with an injection molding machine having a mold clamping of 50 t, and the color flip-flop property on the surface of the molded product was measured.
［比較例１］
実施例１の微粒子酸化亜鉛を添加せずに、同様の方法で樹脂組成物を調製し、且つ同様な方法で成形物表面のカラーフリップフロップ性を測定した。
[Comparative Example 1]
A resin composition was prepared by the same method without adding the fine particle zinc oxide of Example 1, and the color flip-flop property on the surface of the molded product was measured by the same method.
［比較例２］
実施例１の微粒子酸化亜鉛を０．１％添加して、同様の方法で樹脂組成物を調製し、且つ同様な方法で成形物表面のカラーフリップフロップ性を測定した。
[Comparative Example 2]
A resin composition was prepared in the same manner by adding 0.1% of the fine particle zinc oxide of Example 1, and the color flip-flop property on the surface of the molded product was measured in the same manner.
［比較例３］
実施例２の微粒子酸化チタンを添加せずに、同様の方法で樹脂組成物を調製し、且つ同様な方法で成形物表面のカラーフリップフロップ性を測定した。
[Comparative Example 3]
A resin composition was prepared by the same method without adding the fine particle titanium oxide of Example 2, and the color flip-flop property of the surface of the molded product was measured by the same method.
［比較例４］
実施例２のアルミ顔料を０．２％添加して、同様の方法で樹脂組成物を調製し、且つ同様な方法で成形物表面のカラーフリップフロップ性を測定した。
[Comparative Example 4]
0.2% of the aluminum pigment of Example 2 was added to prepare a resin composition by the same method, and the color flip-flop property of the surface of the molded product was measured by the same method.
カラーフリップフロップ性は、Ｘ−ＲＩＴＥ製ＭＡ６８スペクトロフォトメーターにて入射角４５°、正反射に対する受光角１５°と１１０°のＬ*ａ*ｂ*を測定し、その値から下記のようにして算出した（図１参照）。以上の結果を表１に示す。 The color flip-flop property is determined by measuring L * a * b * at an incident angle of 45 ° and light-receiving angles of 15 ° and 110 ° with respect to regular reflection with an MA-68 spectrophotometer manufactured by X-RITE. Calculated (see FIG. 1). The results are shown in Table 1.
なお、Ｌ*ａ*ｂ*は、ＣＩＥのＬＡＢ値を表し、それぞれ、白色標準板の物体色のＪＩＳ Ｚ ８７０１から計算される３刺激値をＸｎ、Ｙｎ、Ｚｎとした試料の相対３刺激値（Ｘ／Ｘｎ）、（Ｙ／Ｙｎ）、（Ｚ／Ｚｎ）を使用して、以下の式から計算され、
Ｌ*＝１１６（Ｙ／Ｙｎ）＾１／３−１６
ａ*＝５００［（Ｘ／Ｘｎ）＾１／３−（Ｙ／Ｙｎ）＾１／３］
ｂ*＝２００［（Ｙ／Ｙｎ）＾１／３−（Ｚ／Ｚｎ）＾１／３］
ΔＬ*、Δａ*、Δｂ*は、ここではそれぞれ、入射角４５°、正反射に対する受光角１５°と１１０°のＬ*ａ*ｂ*値の差の絶対値を表す。なお等色関数間の独立性から数学上、Δａ*の上限値は約１８４、Δｂ*の上限値は約２０１である。 その結果、比較例に対して実施例は、Ｌ*値のみならずａ*値やｂ*値の角度差が大きく、目標どおりのカラーフリップフロップ効果の発現が確認された。
Note that L * a * b * represents the CIE LAB value, and the tristimulus values of the sample with Xn, Yn, and Zn as tristimulus values calculated from JIS Z 8701 of the object color of the white standard plate, respectively. Calculated from the following equation using (X / Xn), (Y / Yn), (Z / Zn):
L * = 116 (Y / Yn) ^ 1 / 3-16
a * = 500 [(X / Xn) ^ 1-3- (Y / Yn) ^ 1/3]
b * = 200 [(Y / Yn) ^ 1-3- (Z / Zn) ^ 1/3]
Here, ΔL * , Δa * , and Δb * represent the absolute value of the difference between the L * a * b * values at the incident angle of 45 ° and the light-receiving angles of 15 ° and 110 ° with respect to regular reflection, respectively. Since the independence between the color matching functions is mathematical, the upper limit value of Δa * is about 184 and the upper limit value of Δb * is about 201. As a result, the Example showed a large angle difference between the a * value and the b * value as well as the L * value, and it was confirmed that the color flip-flop effect was achieved as intended.
本発明によれば、成形物の表面が優れたカラーフリップフロップ効果を有する樹脂組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has the color flip-flop effect in which the surface of the molding was excellent is provided.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009280010A JP5285587B2 (en) | 2009-12-10 | 2009-12-10 | Resin composition for molding and molded product obtained by molding the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009280010A JP5285587B2 (en) | 2009-12-10 | 2009-12-10 | Resin composition for molding and molded product obtained by molding the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011122036A true JP2011122036A (en) | 2011-06-23 |
| JP5285587B2 JP5285587B2 (en) | 2013-09-11 |
Family
ID=44286239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009280010A Active JP5285587B2 (en) | 2009-12-10 | 2009-12-10 | Resin composition for molding and molded product obtained by molding the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5285587B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150022001A (en) * | 2012-06-14 | 2015-03-03 | 가부시키가이샤 구라레 | Multilayer structure, device using same, and manufacturing method therefor |
| JP2015074473A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Lid material for container |
| JP2015074472A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Vertical bag filling sealed bag |
| JP2015074471A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Container including multilayer structure as wall member |
| JP2015074474A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Vacuum packaging bag |
| KR20160134762A (en) | 2014-03-18 | 2016-11-23 | 주식회사 쿠라레 | Multilayer structure and method for producing same, packaging material and product which use same, electronic-device protective sheet, and coating liquid |
| WO2017164234A1 (en) * | 2016-03-22 | 2017-09-28 | 新日鐵住金株式会社 | Precoated metal plate |
| KR20180053735A (en) | 2015-09-17 | 2018-05-23 | 주식회사 쿠라레 | A multilayered structure, a method of manufacturing the same, a packaging material and a product using the same, and a protective sheet of an electronic device |
| JP2020176164A (en) * | 2019-04-15 | 2020-10-29 | 旭化成株式会社 | Brilliant resin composition |
| JPWO2019117055A1 (en) * | 2017-12-15 | 2020-12-17 | 住友電気工業株式会社 | Resin composition for insulating material, insulating material, insulated wire and cable |
| WO2022054709A1 (en) * | 2020-09-14 | 2022-03-17 | 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 | Multi-layer coating film and multi-layer coating film forming method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06254484A (en) * | 1993-03-04 | 1994-09-13 | Kansai Paint Co Ltd | Formation of metallic film |
| JPH07316475A (en) * | 1994-05-20 | 1995-12-05 | Ishihara Sangyo Kaisha Ltd | Coating composition |
| JPH11172202A (en) * | 1997-12-15 | 1999-06-29 | Mitsui Mining & Smelting Co Ltd | Preparation of coated alloy product with excellent corrosion resistance, adhesion and flip-flop properties |
| JPH11279289A (en) * | 1998-03-31 | 1999-10-12 | Unitika Ltd | Resin molded product |
| JP2006321751A (en) * | 2005-05-19 | 2006-11-30 | Tayca Corp | Nail color having high flip-flop effect |
-
2009
- 2009-12-10 JP JP2009280010A patent/JP5285587B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06254484A (en) * | 1993-03-04 | 1994-09-13 | Kansai Paint Co Ltd | Formation of metallic film |
| JPH07316475A (en) * | 1994-05-20 | 1995-12-05 | Ishihara Sangyo Kaisha Ltd | Coating composition |
| JPH11172202A (en) * | 1997-12-15 | 1999-06-29 | Mitsui Mining & Smelting Co Ltd | Preparation of coated alloy product with excellent corrosion resistance, adhesion and flip-flop properties |
| JPH11279289A (en) * | 1998-03-31 | 1999-10-12 | Unitika Ltd | Resin molded product |
| JP2006321751A (en) * | 2005-05-19 | 2006-11-30 | Tayca Corp | Nail color having high flip-flop effect |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150022001A (en) * | 2012-06-14 | 2015-03-03 | 가부시키가이샤 구라레 | Multilayer structure, device using same, and manufacturing method therefor |
| KR101988873B1 (en) | 2012-06-14 | 2019-06-14 | 주식회사 쿠라레 | Multilayer structure, device using same, and manufacturing method therefor |
| JP2015074471A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Container including multilayer structure as wall member |
| JP2015074472A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Vertical bag filling sealed bag |
| JP2015074474A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Vacuum packaging bag |
| JP2015074473A (en) * | 2013-10-09 | 2015-04-20 | 株式会社クラレ | Lid material for container |
| KR20160134762A (en) | 2014-03-18 | 2016-11-23 | 주식회사 쿠라레 | Multilayer structure and method for producing same, packaging material and product which use same, electronic-device protective sheet, and coating liquid |
| KR20180053735A (en) | 2015-09-17 | 2018-05-23 | 주식회사 쿠라레 | A multilayered structure, a method of manufacturing the same, a packaging material and a product using the same, and a protective sheet of an electronic device |
| WO2017164234A1 (en) * | 2016-03-22 | 2017-09-28 | 新日鐵住金株式会社 | Precoated metal plate |
| JPWO2017164234A1 (en) * | 2016-03-22 | 2018-04-12 | 新日鐵住金株式会社 | Pre-coated metal plate |
| JPWO2019117055A1 (en) * | 2017-12-15 | 2020-12-17 | 住友電気工業株式会社 | Resin composition for insulating material, insulating material, insulated wire and cable |
| JP7272276B2 (en) | 2017-12-15 | 2023-05-12 | 住友電気工業株式会社 | Insulating resin composition, insulating material, insulated wire and cable |
| JP2020176164A (en) * | 2019-04-15 | 2020-10-29 | 旭化成株式会社 | Brilliant resin composition |
| WO2022054709A1 (en) * | 2020-09-14 | 2022-03-17 | 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 | Multi-layer coating film and multi-layer coating film forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5285587B2 (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5285587B2 (en) | Resin composition for molding and molded product obtained by molding the same | |
| CN104685015B (en) | Gloss coating composition, method and multilayer film using said composition production multilayer film | |
| JP5392453B2 (en) | Infrared reflective blue pigment, paint and resin composition using the infrared reflective blue pigment | |
| US20120270986A1 (en) | Infrared reflecting black pigment, and paint and resin composition using the infrared reflecting black pigment | |
| JP5907804B2 (en) | Heat discoloration metallic polyamide resin composition | |
| JP5930962B2 (en) | Method for producing surface-treated compression molding material that can be processed in a single screw plastic processing apparatus | |
| KR20180104053A (en) | Polyamide composition containing metallic pigment | |
| AU2018236338A1 (en) | Pelletized thermoplastic pavement marking compositions using glass dust filler | |
| KR20190072123A (en) | Thermoplastic resin composition comprising spherical metal particles and molded article comprising the same | |
| JP5105731B2 (en) | Thermoplastic resin composition for molded articles having flip-flop metallic feeling | |
| KR20150067472A (en) | high gloss polypropylene resin composition and spray free molded product | |
| US20100108947A1 (en) | Resin composition, resin molded article, and generation method of resin composition | |
| JP6647694B2 (en) | Glitter coating composition, glitter coating, and method for forming glitter coating | |
| FI126409B (en) | Compositions containing interactive ingredients | |
| JP4877569B2 (en) | Granular chromatic resin composition | |
| JP2014091819A (en) | Resin composition for injection molding, injection molding article, decorative component, and consumer electronics product using the same | |
| JP5266805B2 (en) | Infrared reflective green pigment, paint and resin composition using the infrared reflective green pigment | |
| JP7000366B2 (en) | Resin composition, resin molded product, and method for manufacturing the resin composition. | |
| JP3894292B2 (en) | Black composite particle powder and paint and resin composition containing the black composite particle powder | |
| JP5948196B2 (en) | White resin composition | |
| JP2009292874A (en) | Resin molded article for place where water is used | |
| JP5494926B2 (en) | Black composite resin particle powder, and paint, resin composition and soft feel paint using the black composite resin particle powder | |
| JP5790892B1 (en) | Resin composition and polyester resin molded body | |
| Schoppe | Aluminum Pigments for Plastics | |
| JP2000319521A (en) | Thermoplastic resin composition for molded article having flipflop metallic appearance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120508 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121011 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121016 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121217 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130205 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20130402 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20130405 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130423 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130528 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130531 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5285587 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |