JP7496467B1 - Colored resin moldings, colored films, colored inks and printing films - Google Patents
Colored resin moldings, colored films, colored inks and printing films Download PDFInfo
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Abstract
【課題】透明樹脂に着色剤を含有させた樹脂成型品であって、光輝剤や蛍光性の染料、顔料を必要とせず、黒下地上の色と白下地上の色とが変化する二色性効果を呈する着色樹脂成型品を提供する。【解決手段】着色樹脂成型品は、透明樹脂、透明樹脂中に含有される高散乱性の赤色着色剤、および透明樹脂中に含有される低散乱性の青色着色剤を有する。D６５光源を用いた１０°視野における黒下地上での色相角が0°～７０°であり、白下地上での前記色相角が２００°～２７０°である。【選択図】 図１[Problem] To provide a resin molding in which a colorant is contained in a transparent resin, which does not require a luminescent agent or a fluorescent dye or pigment, and exhibits a dichroic effect in which the color changes between a black background and a white background. [Solution] The colored resin molding has a transparent resin, a highly scattering red colorant contained in the transparent resin, and a low scattering blue colorant contained in the transparent resin. The hue angle on a black background in a 10° field of view using a D65 light source is 0° to 70°, and the hue angle on a white background is 200° to 270°. [Selected Figure] Figure 1
Description
本発明は、黒い下地上でほぼ赤色から茶色に見え、白い下地上でほぼ青色に見える着色樹脂成型品に関する。 The present invention relates to colored resin moldings that appear mostly red to brown on a black background and mostly blue on a white background.
ガラスを用いた「サフィレット」と呼ばれる人工宝石が知られている。この人工宝石は、見る角度によってブラウンやブルーに変化する微妙な二色性効果を有する。しかし現在、サフィレットの製造方法の知識は失われている。 An artificial gemstone called a "sapphirete" is known, which is made of glass. This gemstone has a subtle dichroic effect, changing color from brown to blue depending on the angle from which it is viewed. However, knowledge of how to make sapphirete has now been lost.
一方、二色性効果を樹脂成型品を用いて再現する方法として、偏光を用いた電圧のオンオフによって発色する液晶性調光フィルムなどが知られている。また、パールなどの光輝材を用いることにより、見る角度や下地色によって色相が変化する二色性効果も知られている。その他にも、下地の色変化に応じて色相を変えることについては、蛍光染顔料でも黄色が緑色方向に変わるといった変動も知られている（特許文献１）。 Meanwhile, a method of reproducing the dichroic effect using resin molded products is known, such as liquid crystal light control films that change color by turning on and off a voltage using polarized light. In addition, a dichroic effect is known in which the hue changes depending on the viewing angle or the base color by using lustrous materials such as pearls. In addition, it is known that fluorescent dye pigments can also change the hue in response to changes in the base color, such as changing from yellow to green (Patent Document 1).
しかし、偏光を用いた液晶性調光については、調光のために電子機器が必要になる。また、パールなどの光輝材や蛍光染顔料を用いた樹脂成型品も、調光には限界があり，また特別な光輝剤を必要とする。このため、透明樹脂に着色剤を含有させた樹脂成型品であって、光輝剤や蛍光染料、蛍光顔料を必要とせず、下地の色のみを変えることにより、サフィレットのような微妙な二色性効果を有する着色樹脂成型品が望まれる。 However, liquid crystal dimming using polarized light requires electronic devices to adjust the light. Also, resin moldings using lustrous materials such as pearls or fluorescent dyes and pigments have limitations in terms of dimming and require special lustrous materials. For this reason, there is a demand for colored resin moldings that contain colorants in transparent resin, and that have a subtle dichroic effect like sapphire by changing only the color of the base, without the need for lustrous materials, fluorescent dyes, or fluorescent pigments.
本発明の課題は、透明樹脂に着色剤を含有させた樹脂成型品であって、光輝剤や蛍光性の染料、顔料を必要とせず、黒下地上の色と白下地上の色とが変化する二色性効果を有する着色樹脂成型品を提供することである。 The objective of the present invention is to provide a colored resin molding that contains a colorant in a transparent resin, does not require luminescent agents or fluorescent dyes or pigments, and has a dichroic effect in which the color changes between a black background and a white background.
本発明に係る着色樹脂成型品は、透明樹脂、前記透明樹脂中に含有される高散乱性の赤色着色剤、および前記透明樹脂中に含有される低散乱性の青色着色剤を有しており、D６５光源を用いた１０°視野における黒下地上での色相角（ｈａｂ：ＣＩＥ１９７６ａ，ｂ ｈｕｅ－ａｎｇｌｅ）が0°～７０°であり、白下地上での前記色相角が２００°～２７０°であることを特徴とする。 The colored resin molding according to the present invention comprises a transparent resin, a highly scattering red colorant contained in the transparent resin, and a low-scattering blue colorant contained in the transparent resin, and is characterized in that the hue angle (h ab : CIE1976a,b hue-angle) on a black background in a 10° field of view using a D65 light source is 0° to 70°, and the hue angle on a white background is 200° to 270°.
また、本発明は、前記着色樹脂成型品からなることを特徴とする、着色フィルムに係るものである。 The present invention also relates to a colored film that is made of the above-mentioned colored resin molding.
また、本発明は、前記着色樹脂成型品を含有することを特徴とする、着色インキに係るものである。 The present invention also relates to a colored ink that contains the colored resin molding.
また、本発明は、前記着色インキの印刷物からなることを特徴とする、印刷フィルムに係るものである。 The present invention also relates to a printed film that is made of the above-mentioned colored ink.
本発明者は、上記課題を解決するために、弁柄（ベンガラ）などの高散乱性の赤色着色剤と、シアニンブルーなどの低散乱性の青色着色剤とを透明樹脂中に混合し、調整することで、黒下地上でほぼ赤色から茶色に見え、白下地上ではほぼ青色に見えるような二色性を示す着色樹脂成型品を作製することに成功した。 To solve the above problem, the inventors mixed and adjusted a highly scattering red colorant such as red iron oxide and a less scattering blue colorant such as cyanine blue into a transparent resin, and succeeded in producing a colored resin molding that exhibits dichroism, appearing almost red to brown on a black background and almost blue on a white background.
（透明樹脂）
「透明樹脂」とは、可視光の反射や吸収が少なく、また樹脂内部で可視光が拡散せずに透過するような樹脂であることが一般に知られている。
透明樹脂としては、熱可塑性樹脂が好ましい。こうした熱可塑性樹脂としては、一般的な樹脂成型品を製造するために用いられる熱可塑性樹脂を用いることができる。熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂；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等のポリエステル樹脂；ポリカーボネート；ポリスチレン；ＡＢＳ；ポリアミド；ポリメチルメタクリレート；ポリウレタン；ポリフェニレンエーテル等を挙げることができる。これらの熱可塑性樹脂は、非晶性の熱可塑性樹脂を用いてもよく、１種単独で又は２種以上を組み合わせて用いることができる。
(transparent resin)
It is generally known that a "transparent resin" is a resin that has little reflection or absorption of visible light and allows visible light to pass through the resin without being diffused.
As the transparent resin, a thermoplastic resin is preferable. As such a thermoplastic resin, a thermoplastic resin used for producing a general resin molded product can be used. As the thermoplastic resin, for example, polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate; polystyrene; ABS; polyamide; polymethyl methacrylate; polyurethane; polyphenylene ether, etc. can be mentioned. As these thermoplastic resins, amorphous thermoplastic resins may be used, and one type alone or two or more types in combination can be used.
透明樹脂は、熱可塑性樹脂以外に、熱硬化性樹脂であってもよい。熱硬化性樹脂としては、例えばウレタン樹脂、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、アルキド樹脂、メラミン樹脂、イミド樹脂、２官能以上のビニル重合性官能基をもつ単量体を重合して得られるスチレン系樹脂や(メタ)アクリレート樹脂等の従来公知の熱硬化性樹脂であってよい。 The transparent resin may be a thermosetting resin in addition to a thermoplastic resin. Examples of the thermosetting resin include urethane resin, epoxy resin, phenol resin, unsaturated polyester resin, vinyl ester resin, alkyd resin, melamine resin, imide resin, styrene resin obtained by polymerizing a monomer having a vinyl polymerizable functional group having two or more functionalities, (meth)acrylate resin, and other conventionally known thermosetting resins.
（高散乱性の赤色着色剤および低散乱性の青色着色剤）
本発明では、透明樹脂中に、高散乱性の赤色着色剤および低散乱性の青色着色剤を含有させることで、黒下地上での色相角と白下地上での色相角を異なる色彩に調整できる。
(Highly scattering red colorant and low scattering blue colorant)
In the present invention, by incorporating a highly scattering red colorant and a low scattering blue colorant in the transparent resin, the hue angle on a black background and the hue angle on a white background can be adjusted to different colors.
ここで、赤色着色剤とは、D６５光源を用いた１０°視野における色相角（ｈａｂ：ＣＩＥ１９７６ａ，ｂ ｈｕｅ－ａｎｇｌｅ）が０°～７０°であることを意味する。赤色着色剤の前記色相角は、２０°以上であることが更に好ましく、また、５０°以下であることが更に好ましい。 Here, the red colorant means a red colorant having a hue angle (h ab : CIE1976a,b hue-angle) of 0° to 70° in a 10° field of view using a D65 light source. The hue angle of the red colorant is more preferably 20° or more, and more preferably 50° or less.
また、青色着色剤とは、D６５光源を用いた１０°視野における色相角（ｈａｂ：ＣＩＥ１９７６ａ，ｂ ｈｕｅ－ａｎｇｌｅ）が１８０°～３６０°であることを意味する。青色着色剤の前記色相角は、２２５°以上であることが更に好ましく、また、３１５°以下であることが更に好ましい。また、各色相角は、後述する樹脂成型品の色相角と同様にして測色するが、この測色の際には、白下地および黒下地は用いない。 Moreover, the blue colorant means that the hue angle (h ab : CIE1976a,b hue-angle) in a 10° visual field using a D65 light source is 180° to 360°. The hue angle of the blue colorant is more preferably 225° or more, and even more preferably 315° or less. Each hue angle is measured in the same manner as the hue angle of a resin molded product described later, but a white or black base is not used during this measurement.
本発明で用いる赤色着色剤は高散乱性であり、青色着色剤は低散乱性である。
ここで、散乱性が低い青色着色剤の場合には、樹脂成型品を光線が透過しなくなるまで青色着色剤を濃厚にすると、樹脂成型品の明度が低くなる。これは青色着色剤の散乱性が低いので、光線の散乱がすくない。このため、樹脂成型品を光線が透過しなくなるようにするためには、青色着色剤の濃度を高くする必要がある。この結果、青色着色剤の濃度が高くなることから、その時点での着色樹脂成型品の明度が低くなるからである。一方、高散乱性の赤色着色剤の場合には、樹脂成型品を光線が透過しなくなるまで濃厚にしても、樹脂成型品の明度が比較的高いままである。これは着色剤の散乱性が高いと、着色剤の濃度が比較的低くとも光線が透過しにくくなる。ゆえに、樹脂成型品を光線が透過しない段階でも明度は比較的に高いままになる。
The red colorant used in the present invention is highly scattering, and the blue colorant is low scattering.
Here, in the case of a blue colorant with low scattering properties, if the blue colorant is concentrated to the point where light does not pass through the resin molded product, the brightness of the resin molded product will be reduced. This is because the blue colorant has low scattering properties, so light rays are not scattered much. Therefore, in order to prevent light rays from passing through the resin molded product, it is necessary to increase the concentration of the blue colorant. As a result, the concentration of the blue colorant increases, and the brightness of the colored resin molded product at that point decreases. On the other hand, in the case of a red colorant with high scattering properties, even if the resin molded product is concentrated to the point where light rays do not pass through it, the brightness of the resin molded product remains relatively high. This is because if the scattering properties of the colorant are high, light rays do not pass through it easily even if the concentration of the colorant is relatively low. Therefore, the brightness remains relatively high even at the stage where light rays do not pass through the resin molded product.
具体的には、各着色剤の散乱性は以下のように測定する。
まず、各着色剤を透明樹脂（透明な軟質塩化ビニル樹脂）中に練り込み、完全には透けていない試験片を作成する。試験片の厚さは１ｍｍとする。ここで、「完全には透けていない試験片」の可視光の全光線透過率は１％以下とする。
Specifically, the scattering property of each colorant is measured as follows.
First, each colorant is mixed into a transparent resin (transparent soft polyvinyl chloride resin) to prepare a test piece that is not completely transparent. The thickness of the test piece is 1 mm. Here, the total light transmittance of the "not completely transparent test piece" is 1% or less.
この状態で、各試験片について、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間に規定される明度（Ｌ＊）を測定する。そして、赤色着色剤の明度（Ｌ＊）が１５以上である場合を「高散乱性」とする。高散乱性の赤色着色剤の明度（Ｌ＊）は、実際上の観点からは、９０以下であることが多い。また、青色着色剤の明度（Ｌ＊）が１０以下である場合を「低散乱性」とする。低散乱性の青色着色剤の明度（Ｌ＊）は、実際上の観点からは、１以上であることが多い。 In this state, the lightness (L * ) of each test piece is measured as defined in the CIE 1976 L*a*b* color space. A red colorant having a lightness (L * ) of 15 or more is considered to be "highly scattering". From a practical standpoint, the lightness (L * ) of a highly scattering red colorant is often 90 or less. A blue colorant having a lightness (L * ) of 10 or less is considered to be "lowly scattering". From a practical standpoint, the lightness (L * ) of a low-scattering blue colorant is often 1 or more.
これらの明度を測色する際には、測定対象である各着色剤を、透明な軟質塩化ビニル樹脂に調合し、厚さ１ｍｍの試験片を作製する。そして、図２に示すように、コニカミノルタ製「ＣＭ－３６ｄＧ」上に各試験片（着色組成物）を設置する。ただし、白下地および黒下地は設けない。具体的な測色条件としては、Ｄ６５光源、視野角１０°で照明径・測定径のサイズにＬＡＶ、測定方式にＳＣＥ方式を用いる。 When measuring these lightness values, each colorant to be measured is mixed into a transparent soft polyvinyl chloride resin to prepare a test piece with a thickness of 1 mm. Then, as shown in Figure 2, each test piece (coloring composition) is placed on a Konica Minolta "CM-36dG." However, no white or black undercoat is provided. Specific color measurement conditions are a D65 light source, a viewing angle of 10°, LAV for the illumination diameter and measurement diameter size, and SCE method for the measurement method.
高散乱性の赤色着色剤としては、黄味弁柄や紫味弁柄のような弁柄類、カドミウム赤、アゾキレート系顔料、不溶性アゾ系顔料、縮合アゾ系顔料、ジケトピロロピロール系顔料、インジゴ顔料、ペリノン系顔料、ペリレン系顔料、キナクリドン系顔料、イソインドリノン系顔料、金属錯体顔料の有機顔料類等を例示できる。
また、低散乱性の青色着色剤としては、α型銅フタロシアニンブルーやβ型銅フタロシアニンブルーなどの銅フタロシアニン類、群青類、コバルトブルー類、青色染料等を例示できる。
Examples of highly scattering red colorants include organic pigments such as red iron oxide such as yellowish red iron oxide and purple iron oxide, cadmium red, azo chelate pigments, insoluble azo pigments, condensed azo pigments, diketopyrrolopyrrole pigments, indigo pigments, perinone pigments, perylene pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments.
Examples of low-scattering blue colorants include copper phthalocyanines such as α-type copper phthalocyanine blue and β-type copper phthalocyanine blue, ultramarine blues, cobalt blues, blue dyes, and the like.
（着色樹脂成型品の色相角）
本発明においては、図１の模式図に示すように、D６５光源を用いた１０°視野における黒下地上での樹脂成型品の色相角（ｈａｂ：ＣＩＥ１９７６ａ，ｂ ｈｕｅ－ａｎｇｌｅ）が0°～７０°であり、白下地上での色相角が２００°～２７０°である。すなわち、本発明の樹脂成型品は、黒下地上と白下地上で顕著な色相角差を有しており、二色性を発現するものである。
更には、本発明の樹脂成型品は、白下地上と同様に、透過色での色相角も２００°～２７０°とすることが可能である。
(Hue angle of colored resin moldings)
In the present invention, as shown in the schematic diagram of Figure 1, the hue angle (h ab : CIE1976a,b hue-angle) of the resin molding on a black background in a 10° field of view using a D65 light source is 0° to 70°, and the hue angle on a white background is 200° to 270°. In other words, the resin molding of the present invention has a significant difference in hue angle between the black background and the white background, and exhibits dichroism.
Furthermore, the resin molding of the present invention can achieve a hue angle of 200° to 270° in transmitted color, similar to that over a white background.
着色樹脂成型品の色相角は以下のようにして測定する。
すなわち、測定対象である各着色剤を、透明な軟質塩化ビニル樹脂に調合し、厚さ１ｍｍの試験片を作製する。そして、図２に示すように、コニカミノルタ製「ＣＭ－３６ｄＧ」上に各試験片（着色組成物）を設置する。そして、各試験片と測定部との間に、白下地（エバーズＥＶＥＲ－ＷＨＩＴＥ９５８２）または黒下地（ＥＶＥＲ－ＢＬＡＣＫ０００５）を介在させ、測色を実施する。
具体的な測色条件としては、照明径・測定径のサイズにＬＡＶ、測定方式にＳＣＥ方式を用いる。
The hue angle of a colored resin molding is measured as follows.
That is, each colorant to be measured is mixed with a transparent soft polyvinyl chloride resin to prepare a test piece having a thickness of 1 mm. Then, as shown in FIG. 2, each test piece (coloring composition) is placed on a Konica Minolta "CM-36dG". Then, a white undercoat (EVER's EVER-WHITE 9582) or a black undercoat (EVER-BLACK 0005) is placed between each test piece and the measurement part, and color measurement is performed.
As specific color measurement conditions, the illumination diameter and measurement diameter are set to LAV, and the measurement method is set to SCE method.
好適な実施形態においては、黒下地上および白下地上での樹脂成型品の各彩度（Ｃ＊ａｂ：ＣＩＥ１９７６ ａ，ｂ ｃｈｒｏｍａ）をそれぞれ３以上、１５０以下とする。 In a preferred embodiment, the chroma (C *ab : CIE1976 a, b chroma) of a resin molding on a black background and that on a white background are set to 3 or more and 150 or less, respectively.
一般に色調を表す方法として、国際照明委員会（ＣＩＥ）が策定した、目で見える色を色空間として表現する、ＣＩＥ Ｌ＊ａ＊ｂ＊表色系（色空間）がある（図１参照）。このＣＩＥ Ｌ＊ａ＊ｂ＊表色系においては、色を３つの座標で表現し、明度が「Ｌ＊」、赤（マゼンタ）～緑が「ａ＊」（正がマゼンタ、負が緑味）、黄～青を「ｂ＊」（正が黄味、負が青味）にそれぞれ対応する。 A common method of expressing color tone is the CIE L * a * b * color system (color space), which was established by the International Commission on Illumination (CIE) to express colors that can be seen with the naked eye as a color space (see Figure 1). In this CIE L*a*b* color system, colors are expressed using three coordinates: lightness corresponds to "L*", red (magenta) to green corresponds to "a*" (positive is magenta, negative is greenish), and yellow to blue corresponds to "b*" (positive is yellowish, negative is blueish).
実際に透明樹脂中に各種着色剤を練り込んで見た結果、白下地上で有彩色であった場合（つまり彩度がある程度高い場合）には、黒下地上では白下地上と類似の色相になる場合が多く、あるいは黒下地上では彩度の低い黒い色となることが多いことがわかった。これに対して、本発明の樹脂成型品は、白下地上でも黒下地上でもある程度高い彩度を示すことができるものであった。具体的には、黒下地上および白下地上での樹脂成型品の各彩度（Ｃ＊ａｂ：ＣＩＥ１９７６ ａ，ｂ ｃｈｒｏｍａ）をそれぞれ３以上、１５０以下とする。これら各彩度は、３以上であることが更に好ましく、また２０以下であることが更に好ましい。 As a result of actually kneading various colorants into a transparent resin, it was found that when a color was chromatic on a white background (i.e., when the saturation was somewhat high), on a black background it often had a similar hue to that on a white background, or on a black background it often had a low saturation black color. In contrast, the resin molded product of the present invention was able to exhibit a relatively high saturation on both a white background and a black background. Specifically, the saturations (C *ab : CIE1976 a, b chroma) of the resin molded product on a black background and on a white background are set to 3 or more and 150 or less, respectively. It is more preferable that each of these saturations is 3 or more, and more preferably 20 or less.
これら彩度を測定するには、各着色樹脂成型品の測色と同様にして、図２に示すようにして測定する。 To measure these saturations, they are measured in the same way as the colorimetric measurements of each colored resin molding, as shown in Figure 2.
樹脂成型品における各成分の好適比率を以下に示す。
（１） 高散乱性の赤色着色剤の質量を１．０００とした場合：
低散乱性の青色着色剤の質量は０．０４０～０．５００が好ましく、０．０４５～０．４００が更に好ましく、０．０５０～０．３２０が特に好ましい。また、透明樹脂の質量は、８００～５０００が好ましく、９００～４５００が更に好ましく、１０００～４０００が特に好ましい。
The preferred ratios of each component in the resin molded product are shown below.
(1) When the mass of the highly scattering red colorant is 1.000:
The mass of the low-scattering blue colorant is preferably 0.040 to 0.500, more preferably 0.045 to 0.400, and particularly preferably 0.050 to 0.320. The mass of the transparent resin is preferably 800 to 5000, more preferably 900 to 4500, and particularly preferably 1000 to 4000.
（２） 赤色着色剤の前記明度（Ｌ＊）が２５以上であり、質量を１．０００とした場合
低散乱性の青色着色剤の質量は０．０４０～０．５００が好ましく、０．０４５～０．４００が更に好ましく、０．１００～０．３２０が特に好ましい。また、透明樹脂の質量は、８００～５０００が好ましく、９００～４５００が更に好ましく、１０００～４０００が特に好ましい。
(2) When the lightness (L * ) of the red colorant is 25 or more and the mass is 1.000, the mass of the low-scattering blue colorant is preferably 0.040 to 0.500, more preferably 0.045 to 0.400, and particularly preferably 0.100 to 0.320. The mass of the transparent resin is preferably 800 to 5000, more preferably 900 to 4500, and particularly preferably 1000 to 4000.
（３） 赤色着色剤の前記明度（Ｌ＊）が１５以上、２５未満（特には２４．９９９以下）であり、質量を１．０００とした場合
低散乱性の青色着色剤の質量は０．０４０～０．５００が好ましく、０．０４５～０．４００が更に好ましく、０．０５０～０．３２０が特に好ましい。また、透明樹脂の質量は、８００～５０００が好ましく、９００～４５００が更に好ましく、１０００～４０００が特に好ましい。
(3) When the lightness (L * ) of the red colorant is 15 or more and less than 25 (particularly 24.999 or less) and the mass is 1.000, the mass of the low-scattering blue colorant is preferably 0.040 to 0.500, more preferably 0.045 to 0.400, and particularly preferably 0.050 to 0.320. The mass of the transparent resin is preferably 800 to 5000, more preferably 900 to 4500, and particularly preferably 1000 to 4000.
（他の添加剤）
本発明の着色樹脂成型品は、本発明の趣旨を逸脱しない範囲で、他の添加剤を含有してもよい。例えば、分散剤、酸化防止剤、安定剤、紫外線吸収剤、滑剤、加工助剤、帯電防止剤、耐衝撃助剤、充填剤、艶消し剤などが含有されていてもよい。着色樹脂成型品中に含まれる樹脂の量を１００質量部としたとき、他の添加剤の含有量は５質量部以下が好ましく、０質量部であってもよい。
(Other Additives)
The colored resin molding of the present invention may contain other additives within the scope of the present invention. For example, dispersants, antioxidants, stabilizers, ultraviolet absorbers, lubricants, processing aids, antistatic agents, impact resistance aids, fillers, matting agents, etc. may be contained. When the amount of resin contained in the colored resin molding is taken as 100 parts by mass, the content of other additives is preferably 5 parts by mass or less, and may be 0 parts by mass.
（着色樹脂成型品の製造）
本発明の着色樹脂成型品は、一般に、樹脂と着色剤とを、バンバリーミキサー、ナウターミキサー、混練ロール、又は一軸、二軸押し出し機などにより、溶融混合、分散処理することによって、得ることが出来る。また混練前に分散均一化する目的で、タンブラーミキサー、ブレンダー、高速混合機で予備分散を行ってもよい。
(Manufacturing of colored resin molded products)
The colored resin molding of the present invention can generally be obtained by melt mixing and dispersing the resin and the colorant using a Banbury mixer, a Nauta mixer, a kneading roll, or a single-screw or twin-screw extruder, etc. Furthermore, for the purpose of uniformly dispersing the resin and the colorant before kneading, preliminary dispersion may be performed using a tumbler mixer, a blender, or a high-speed mixer.
得られた着色樹脂成型品の成形方法としては、限定されないが、射出成形、射出圧縮成形、圧空成形、ブロー成形、真空成形、発泡成形、押し出し成形等の公知の方法で、所定の形状に成形される。このとき、目的に応じて熱安定剤，耐候安定剤，滑剤，顔料分散剤，静電気防止剤などの添加剤を添加することができる。また、高意匠性等、成形物に必要な目的に応じて、他の顔料や染料を添加することができる。 The resulting colored resin molded product can be molded into a desired shape by known methods such as, but not limited to, injection molding, injection compression molding, compressed air molding, blow molding, vacuum molding, foam molding, and extrusion molding. At this time, additives such as heat stabilizers, weather stabilizers, lubricants, pigment dispersants, and antistatic agents can be added depending on the purpose. In addition, other pigments and dyes can be added depending on the purpose required for the molded product, such as high designability.
成形機を使用し、一般的なフィルム成形方法やシート成形方法によって着色樹脂成型品を成形することで、フィルム状又はシート状の成形体を製造することができる。成形機としては、押出成形機、中空成形機、真空成形機、圧空成形機、圧縮成形機、カレンダー成形機等を使用することができる。フィルム状成形体及びシート状成形体の厚みは、用途に応じて適宜調整すればよい。具体的には、０．１～５００μｍとすることが好ましく、１～１００μｍとすることがさらに好ましい。 A film- or sheet-shaped molded product can be produced by using a molding machine to mold a colored resin molded product using a general film molding method or sheet molding method. Examples of molding machines that can be used include extrusion molding machines, blow molding machines, vacuum molding machines, compressed air molding machines, compression molding machines, and calendar molding machines. The thickness of the film-shaped molded product and sheet-shaped molded product can be adjusted appropriately depending on the application. Specifically, the thickness is preferably 0.1 to 500 μm, and more preferably 1 to 100 μm.
積層フィルムを共押出成形する場合は、各層を構成する樹脂が、それぞれ加熱溶融され、異なる押出機やポンプ等からそれぞれの流路を通って押出ダイに供給され、押出ダイから多層に押し出された後に接着する。この押出ダイとしては、例えばマルチマニホールドダイ、フィードブロック等のＴダイを用いることができる。 When co-extrusion molding a laminated film, the resins that make up each layer are heated and melted, and then fed to an extrusion die through separate flow paths from different extruders, pumps, etc., and are bonded together after being extruded in multiple layers from the extrusion die. For example, a multi-manifold die, a feed block, or other T-die can be used as the extrusion die.
また、紡糸機を使用して着色樹脂成型品を紡糸することで、繊維状の成形体を製造することができる。繊維状の成形体の繊維径は、用途に応じて適宜調整すればよい。具体的には、１～１，０００μｍとすることが好ましく、１～５００μｍとすることがさらに好ましく、５～２００μｍとすることが特に好ましい。繊維状の成形体は、適当な長さに裁断してもよいし、束ねて繊維束としてもよい。さらに、布や不織布に加工することもできる。 Fiber-like molded products can also be produced by spinning colored resin moldings using a spinning machine. The fiber diameter of the fibrous molded products can be adjusted appropriately depending on the application. Specifically, it is preferably 1 to 1,000 μm, more preferably 1 to 500 μm, and particularly preferably 5 to 200 μm. The fibrous molded products can be cut to an appropriate length or bundled into fiber bundles. They can also be processed into cloth or nonwoven fabric.
（本発明の着色樹脂成型品の好適な用途）
本発明の着色成型品は、二色性を有しているので、二色性を利用している多種類の用途に好適に利用できる。すなわち、二色性を意匠や装飾として利用する用途に広く利用可能であり、各種部品、容器外面に形成できる。また、二色性を有する特殊な性質を持つことから、偽造防止部材への使用が期待される。
(Suitable uses of the colored resin molding of the present invention)
The colored molded product of the present invention has dichroism, and therefore can be suitably used in a wide variety of applications that utilize dichroism. In other words, it can be widely used in applications that utilize dichroism as design or decoration, and can be formed on the outer surfaces of various parts and containers. In addition, because it has the special property of dichroism, it is expected to be used as an anti-counterfeiting material.
具体的には、例えば、本発明の着色樹脂成型品からなる着色フィルムは、各種物体に対してはりつけることができる。
また、本発明の着色樹脂成型品を含有する着色インキは、各種物体に印刷することで、二色性を有する印刷フィルムを形成することができる。こうした着色インキには、種々の有機溶媒および各種の公知添加剤を含有させることができる。
Specifically, for example, a colored film made of the colored resin molding of the present invention can be attached to various objects.
In addition, the colored ink containing the colored resin molding of the present invention can be printed on various objects to form a printed film having dichroism. Such colored ink can contain various organic solvents and various known additives.
（各着色剤）
表１に示す各着色剤を用意した。ただし、各着色剤の前記明度（Ｌ＊）および色相角を測定し、表１に示す。
(Each colorant)
The colorants shown in Table 1 were prepared. The lightness (L * ) and hue angle of each colorant were measured and are shown in Table 1.
（本発明実施例および比較例の着色樹脂成型品の製造）
表２に示す各例の配合の各着色剤と透明軟質ビニル樹脂とを混合し、ロール成形することで、各樹脂成型品を製造した。ただし、各着色剤を効率よく分散させるため、予め加工した塩化ビニル樹脂用潤性粉末着色剤ディスコールを使用した。厚さ１ｍｍの着色樹脂成型品を製造した。ただし、表２に示す数値は、赤色着色剤の質量を１．０００としたときの各成分の質量比率を示す。
(Production of colored resin moldings of examples of the present invention and comparative examples)
Each resin molded product was manufactured by mixing each colorant in the formulation shown in Table 2 with transparent soft vinyl resin and roll molding it. However, in order to efficiently disperse each colorant, a pre-processed moisturizing powder colorant for polyvinyl chloride resin, Discol, was used. A colored resin molded product with a thickness of 1 mm was manufactured. However, the values shown in Table 2 indicate the mass ratio of each component when the mass of the red colorant is 1.000.
（各着色樹脂成型品の測色結果）
白下地・黒下地上での各着色樹脂成型品の測色を前述のようにして行った。そして、Ｄ６５光源、１０°視野でのＣＩＥ１９７６によるＬ＊ａ＊ｂ＊色空間のＣ＊ａｂ、hａｂを算出し、その結果を表3に示す。
(Color measurement results for each colored resin molding)
The colorimetry of each colored resin molding on a white and black background was carried out as described above. Then, C* ab and h ab in the L*a*b* color space according to CIE1976 with a D65 light source and a 10° field of view were calculated, and the results are shown in Table 3.
表3より、白下地と黒下地での色差（ΔＥ＊： ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊ｃｏｌｏｕｒ ｄｉｆｆｒｅｎｃｅ）、Δｈａｂ、色相差（ΔＨ＊ ａｂ：ＣＩＥ １９７６ ａ，ｂ ｈｕｅ－ｄｉｆｆｅｒｅｎｃｅ）を算出し、その結果を表4に示す。 From Table 3, the color difference (ΔE * : CIE 1976 L*a*b* colour difference), Δh ab and hue difference (ΔH * ab : CIE 1976 a,b hue-difference) between the white and black backgrounds were calculated. The results are shown in Table 4.
実施例１～４の着色樹脂成型品は、白下地上ではほぼ青色、黒下地ではほぼ赤色から茶色に目視することが出来る程、彩度が高く（Ｃ＊ ａｂ＞＞３．００）、その色相角ｈａｂの差Δｈａｂは１４０°以上に達している。すなわち、下地の色を変えることにより、着色樹脂成型品の色相が大きく変化し、顕著な二色性を示すことに成功した。 The colored resin moldings of Examples 1 to 4 have such high chroma (C * ab >>3.00) that they appear almost blue on a white background and almost red to brown on a black background, and the difference in hue angle h ab , Δh ab , reaches 140° or more. In other words, by changing the color of the background, the hue of the colored resin moldings changes significantly, and they successfully exhibit remarkable dichroism.
比較例１の着色樹脂成型品、比較例２の着色樹脂成型品では、顕著な二色性は示されなかった。 The colored resin molded products of Comparative Example 1 and Comparative Example 2 did not exhibit significant dichroism.
実施例５は、実施例１～４の黄味弁柄を紫味弁柄に変更した例である。この場合にも顕著な二色性を達成することに成功した。 Example 5 is an example in which the yellowish iron oxide of Examples 1 to 4 is changed to a purple iron oxide. In this case too, we were successful in achieving significant dichroism.
実施例6は、実施例１～４のβ型銅フタロシアニンブルーを変更し、黄味弁柄とα型銅フタロシアニンブルーを配合した着色樹脂成型品である。また、実施例7は、実施例１～４の赤色着色剤、青色着色剤の両方を変更した例である。いずれも顕著な二色性を達成することに成功した。 Example 6 is a colored resin molding in which the β-type copper phthalocyanine blue of Examples 1 to 4 is replaced with a mixture of yellowish red iron oxide and α-type copper phthalocyanine blue. Example 7 is an example in which both the red and blue colorants of Examples 1 to 4 are replaced. In both cases, we succeeded in achieving significant dichroism.
比較例3は、黄味弁柄のみを配合した着色樹脂成型品であり、低散乱性の青色着色剤が配合されてない。この場合には、着色樹脂成型品は二色性を示さなかった。 Comparative Example 3 is a colored resin molding containing only yellowish red iron oxide, and no low-scattering blue colorant. In this case, the colored resin molding did not exhibit dichroism.
Claims (7)
A colored resin molding comprising a transparent resin, a highly scattering red colorant contained in said transparent resin, and a low scattering blue colorant contained in said transparent resin, the colored resin molding having a hue angle of 0° to 70° on a black background in a 10° field of view using a D65 light source and a hue angle of 200° to 270° on a white background.
2. The colored resin molding according to claim 1, wherein the chroma on a black background and the chroma on a white background are 3 or more and 150 or less, respectively.
3. The colored resin molding according to claim 1, wherein the red colorant is red iron oxide.
3. The colored resin molding according to claim 1, wherein the blue colorant is a phthalocyanine colorant.
A colored film comprising the colored resin molding according to claim 1 or 2.
A colored ink comprising the colored resin molding according to claim 1 or 2.
A printed film comprising a print of the colored ink according to claim 6.
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| JP2004511636A (en) | 2000-10-18 | 2004-04-15 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Low color dark curable composition |
| JP2008527052A (en) | 2004-01-21 | 2008-07-24 | チバ ホールディング インコーポレーテッド | Dye mixture |
| JP2010520929A (en) | 2007-02-23 | 2010-06-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Transparent colorants and colorant compositions and their use |
| JP2013534945A (en) | 2010-06-14 | 2013-09-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Black dichroic dye |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004511636A (en) | 2000-10-18 | 2004-04-15 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Low color dark curable composition |
| JP2008527052A (en) | 2004-01-21 | 2008-07-24 | チバ ホールディング インコーポレーテッド | Dye mixture |
| JP2010520929A (en) | 2007-02-23 | 2010-06-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Transparent colorants and colorant compositions and their use |
| JP2013534945A (en) | 2010-06-14 | 2013-09-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Black dichroic dye |
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