JP2020125376A - Resin composition, resin molding, and method for producing resin composition - Google Patents
Resin composition, resin molding, and method for producing resin composition Download PDFInfo
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本発明は、樹脂組成物、樹脂成形体、及び樹脂組成物の製造方法に関する。 The present invention relates to a resin composition, a resin molded product, and a method for producing a resin composition.
自動車分野、電子機器分野、及び家電分野等の各種成形体を構成する材料として、取り扱い容易な樹脂組成物が用いられている。また、コスト、成形性、及び機械物性等の観点から、ポリエチレンやポリプロピレン等のポリオレフィン樹脂が樹脂組成物の基材（ベース樹脂）として用いられている。 A resin composition that is easy to handle is used as a material for forming various molded products in the fields of automobiles, electronic devices, and home appliances. Further, from the viewpoint of cost, moldability, mechanical properties, etc., polyolefin resins such as polyethylene and polypropylene are used as the base material (base resin) of the resin composition.
近年、上記の機械物性等以外の特性として、デザイナーや需要者のニーズに応えるための意匠性が付与された各種の成形体を製造しうる樹脂組成物が必要とされている。なかでも、青味で黒色度の高い、いわゆる漆黒性の色調が高いニーズを占めている。成形体表面に漆黒性を付与する方法として、例えば、成形体表面に塗料を塗布する方法（塗装方法）がある。しかし、コスト及び環境に対する影響等の配慮から、塗装方法によらず、黒色を呈する着色成分の練り込みによって成形体を着色することが要求されている。樹脂を黒色に着色する際には、カーボンブラックやペリレンブラック等の黒色顔料の他、アゾ系化合物やアジン系化合物等の黒色染料を用いることがある。しかし、黒色染料は、樹脂の種類によってはブリードすることがあるため、ブリードの恐れのないカーボンブラックを用いることが一般的である。 In recent years, there has been a demand for a resin composition capable of producing various molded articles having properties other than the above mechanical properties and the like, which are designed to meet the needs of designers and consumers. Of these, the so-called jet black color tone, which is bluish and has a high degree of blackness, occupies a high need. As a method of imparting jet-blackness to the surface of the molded body, there is, for example, a method of applying a paint to the surface of the molded body (painting method). However, from the viewpoint of cost and environmental impact, it is required to color the molded body by kneading a coloring component exhibiting a black color regardless of the coating method. When the resin is colored black, black pigments such as azo compounds and azine compounds may be used in addition to black pigments such as carbon black and perylene black. However, since the black dye may bleed depending on the type of resin, it is common to use carbon black that does not cause bleeding.
カーボンブラックは、通常、粒径が小さいほど黒色度が高いが赤味が強く、粒径が大きいほど青味を帯びている。すなわち、粒径を基準とした場合、カーボンブラックの青味と黒色度はトレードオフの関係にある。このため、カーボンブラックを用いて、青味で黒色度の高い、いわゆる漆黒性の色調を有する樹脂成形体、及びその成形原料となる樹脂組成物を製造することは一般的に困難であった。なお、フタロシアニンブルーや群青等の微量の青色顔料をカーボンブラックと併用して青味を付与する手法もある。しかし、青色顔料を併用すると、黒色度が低下しやすくなるとともに、直射日光下で赤味が浮いて観察される、いわゆるブロンズ現象が発生しやすくなる等の新たな課題が生ずる。 Carbon black generally has a higher degree of blackness as the particle size is smaller, but has a stronger reddish color, and has a bluish color as the particle size is larger. That is, based on the particle size, the bluishness and the blackness of carbon black have a trade-off relationship. Therefore, it has been generally difficult to produce a resin molded product having a so-called jet black color tone having a bluish color and a high degree of blackness using carbon black, and a resin composition serving as a molding raw material thereof. There is also a method of imparting a bluish color by using a small amount of a blue pigment such as phthalocyanine blue or ultramarine blue in combination with carbon black. However, when a blue pigment is used in combination, a new problem arises in that the blackness is likely to decrease and the reddishness is observed under direct sunlight, so-called bronze phenomenon easily occurs.
漆黒性の高い樹脂組成物やその成形体を提供すべく、例えば、ポリエステルと、一次粒子径の異なる複数種のカーボンブラックとを含有する原着繊維用の樹脂組成物が提案されている（特許文献１）。また、ポリオレフィン等の樹脂と、カーボンナノチューブとを含有する樹脂組成物が提案されている（特許文献２及び３）。 In order to provide a resin composition having high jet blackness and a molded body thereof, for example, a resin composition for a primary fiber containing a polyester and a plurality of types of carbon black having different primary particle diameters has been proposed (Patent Reference 1). Further, a resin composition containing a resin such as polyolefin and carbon nanotubes has been proposed (Patent Documents 2 and 3).
しかし、特許文献１で提案された樹脂組成物はΔＬ＊値やΔｂ＊値の変化量が小さく、さほど漆黒性が向上したものであるとは言えなかった。また、特許文献２及び３で提案された樹脂組成物は、高価なカーボンナノチューブを着色剤として用いたものであることから、コスト面等でさらなる改良の余地がある。さらに、カーボンナノチューブを樹脂中に分散させることは困難であるといった課題があった。 However, the resin composition proposed in Patent Document 1 has a small amount of change in the ΔL * value and the Δb * value, and it cannot be said that the jet black property is improved so much. Further, since the resin compositions proposed in Patent Documents 2 and 3 use expensive carbon nanotubes as a coloring agent, there is room for further improvement in cost and the like. Further, there is a problem that it is difficult to disperse the carbon nanotubes in the resin.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、青味で黒色度の高い、いわゆる漆黒性に優れた樹脂成形体を製造するための原料として有用な樹脂組成物を提供することにある。また、本発明の課題とするところは、上記の樹脂組成物を用いて製造される漆黒性に優れた樹脂成形体を提供することにある。さらに、本発明の課題とするところは、カーボンブラックを着色剤としながらも漆黒性が向上した樹脂組成物の製造方法を提供することにある。 The present invention has been made in view of the problems of such conventional techniques, and the problem is to produce a resin molded article having a high bluish blackness and excellent so-called jet blackness. The purpose of the present invention is to provide a resin composition useful as a raw material. Moreover, the place made into the subject of this invention is providing the resin molded body excellent in jet black produced using the said resin composition. A further object of the present invention is to provide a method for producing a resin composition having improved jet blackness while using carbon black as a colorant.
すなわち、本発明によれば、以下に示す樹脂組成物が提供される。
［１］透明又は半透明の熱可塑性樹脂、カーボンブラック、及び光拡散剤を含有し、前記熱可塑性樹脂の屈折率ｎ１と前記光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）が、０を超えて０．１２未満であり、前記光拡散剤の平均粒子径が、０．３μｍ未満である樹脂組成物。
［２］下記式（１）及び（２）の関係を満たす前記［１］に記載の樹脂組成物。
ΔＬ＊≦−０．３ ・・・（１）
Δｂ＊≦−０．１５ ・・・（２）
ΔＬ＊：樹脂組成物のＬ＊値から、前記光拡散剤を含有しないこと以外は前記樹脂組成物と同一の組成である基準組成物のＬ＊値を減じた値
Δｂ＊：樹脂組成物のｂ＊値から、前記光拡散剤を含有しないこと以外は前記樹脂組成物と同一の組成である基準組成物のｂ＊値を減じた値
［３］樹脂成形体を成形する成形材料として用いられる前記［１］又は［２］に記載の樹脂組成物。
［４］前記カーボンブラックの含有量が、前記熱可塑性樹脂１００質量部に対して、０．０２５〜３質量部であり、前記光拡散剤の含有量が、前記熱可塑性樹脂１００質量部に対して、０．０２５〜１２質量部である前記［３］に記載の樹脂組成物。
［５］ベース樹脂を着色するマスターバッチとして用いられる前記［１］又は［２］に記載の樹脂組成物。
［６］前記カーボンブラックの含有量が、前記熱可塑性樹脂１００質量部に対して、１〜８０質量部であり、前記光拡散剤の含有量が、前記熱可塑性樹脂１００質量部に対して、１〜８０質量部である前記［５］に記載の樹脂組成物。
That is, according to the present invention, the following resin composition is provided.
[1] An absolute value (|n of the difference between the refractive index n 1 of the thermoplastic resin and the refractive index n 2 of the light diffusing agent, which contains a transparent or translucent thermoplastic resin, carbon black, and a light diffusing agent. 1- n 2 |) is more than 0 and less than 0.12, and the average particle diameter of the light diffusing agent is less than 0.3 μm.
[2] The resin composition according to [1], which satisfies the relationships of the following formulas (1) and (2).
ΔL * ≦−0.3 (1)
Δb * ≦−0.15 (2)
[Delta] L *: the L * value of the resin composition, a value obtained by subtracting the L * value of the reference composition except that it does not contain the same composition as the resin composition of the light diffusing agent [Delta] b *: the resin composition A value obtained by subtracting the b * value of a reference composition having the same composition as the resin composition from the b * value except that the light diffusing agent is not included. [3] Used as a molding material for molding a resin molded body The resin composition according to the above [1] or [2].
[4] The content of the carbon black is 0.025 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and the content of the light diffusing agent is 100 parts by mass of the thermoplastic resin. The resin composition according to the above [3], which is 0.025 to 12 parts by mass.
[5] The resin composition according to the above [1] or [2], which is used as a masterbatch for coloring a base resin.
[6] The content of the carbon black is 1 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and the content of the light diffusing agent is 100 parts by mass of the thermoplastic resin. The resin composition according to the above [5], which is 1 to 80 parts by mass.
また、本発明によれば、以下に示す樹脂成形体が提供される。
［７］前記［１］〜［４］のいずれかに記載の樹脂組成物の成形物である樹脂成形体。
Further, according to the present invention, the following resin molded body is provided.
[7] A resin molded product that is a molded product of the resin composition according to any one of [1] to [4].
さらに、本発明によれば、以下に示す樹脂組成物の製造方法が提供される。
［８］透明又は半透明の熱可塑性樹脂、カーボンブラック、及び光拡散剤を含む原材料を混合して樹脂組成物を得る工程を有し、前記熱可塑性樹脂の屈折率ｎ１と前記光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）が、０を超えて０．１２未満であり、前記光拡散剤の平均粒子径が、０．３μｍ未満である、漆黒性が向上した樹脂組成物の製造方法。
Furthermore, according to the present invention, the following method for producing a resin composition is provided.
[8] A step of mixing a transparent or semitransparent thermoplastic resin, carbon black, and a raw material containing a light diffusing agent to obtain a resin composition, wherein the refractive index n 1 of the thermoplastic resin and the light diffusing agent are included. The absolute value of the difference in refractive index n 2 (|n 1 −n 2 |) is more than 0 and less than 0.12, and the average particle diameter of the light diffusing agent is less than 0.3 μm. Of producing a resin composition having improved properties.
本発明によれば、青味で黒色度の高い、いわゆる漆黒性に優れた樹脂成形体を製造するための原料として有用な樹脂組成物を提供することができる。また、本発明によれば、上記の樹脂組成物を用いて製造される漆黒性に優れた樹脂成形体を提供することができる。さらに、本発明によれば、カーボンブラックを着色剤としながらも漆黒性が向上した樹脂組成物の製造方法を提供することができる。 According to the present invention, it is possible to provide a resin composition which is useful as a raw material for producing a resin molded body that is bluish and has a high degree of blackness and is excellent in so-called jet blackness. Further, according to the present invention, it is possible to provide a resin molded article manufactured using the above resin composition and having excellent jet blackness. Furthermore, according to the present invention, it is possible to provide a method for producing a resin composition having improved jet blackness while using carbon black as a colorant.
＜樹脂組成物＞
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。本発明の一実施形態である樹脂組成物は、透明又は半透明の熱可塑性樹脂、カーボンブラック、及び光拡散剤を含有する。そして、熱可塑性樹脂の屈折率ｎ１と光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）は、０を超えて０．１２未満である。また、光拡散剤の平均粒子径は、０．３μｍ未満である。
<Resin composition>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The resin composition which is one embodiment of the present invention contains a transparent or translucent thermoplastic resin, carbon black, and a light diffusing agent. Then, the absolute value of the difference between the refractive index n 2 of the refractive index n 1 and the light diffusing agent of the thermoplastic resin (| n 1 -n 2 |) is less than 0.12 greater than zero. The average particle size of the light diffusing agent is less than 0.3 μm.
一般的な光拡散剤は、ＬＥＤ光源から照射される光等の指向性の強い光を拡散させるべく、照明器具用のカバー材等を構成する樹脂材料に配合される粉末状又は粒子状の成分である。すなわち、光拡散剤は光を透過・拡散させる部材用の樹脂材料に配合される成分であるため、光を吸収するカーボンブラック等の黒色の着色剤との併用は一般的には想定されていない。本発明者らは、透明又は半透明の熱可塑性樹脂に、その屈折率（ｎ２）が熱可塑性樹脂の屈折率（ｎ１）と異なる光拡散剤をカーボンブラックとともに配合することについて検討した。その結果、驚くべきことに、得られた樹脂組成物の漆黒性が、光拡散剤を配合せずにカーボンブラックのみを配合したものに比して顕著に向上することを見出した。好ましくは、本実施形態の樹脂組成物は下記式（１）及び（２）の関係を満たすものである。なお、本明細書におけるＬ＊値、ａ＊値、及びｂ＊値は、ＣＩＥ ＬＡＢ（Ｌ＊ａ＊ｂ＊）表色系におけるＬ＊値、ａ＊値、及びｂ＊値を意味する。
ΔＬ＊≦−０．３ ・・・（１）
Δｂ＊≦−０．１５ ・・・（２）
ΔＬ＊：樹脂組成物のＬ＊値から、光拡散剤を含有しないこと以外は樹脂組成物と同一の組成である基準組成物のＬ＊値を減じた値
Δｂ＊：樹脂組成物のｂ＊値から、光拡散剤を含有しないこと以外は樹脂組成物と同一の組成である基準組成物のｂ＊値を減じた値
A general light diffusing agent is a powder-like or particle-like component that is mixed with a resin material that constitutes a cover material for lighting fixtures in order to diffuse highly directional light such as light emitted from an LED light source. Is. That is, since the light diffusing agent is a component mixed in the resin material for the member that transmits/diffuses light, it is generally not supposed to be used in combination with a black colorant such as carbon black that absorbs light. .. The present inventors have found that a transparent or translucent thermoplastic resin, was examined for its refractive index (n 2) is formulated refractive index of the thermoplastic resin and the different light diffusing agent (n 1) with carbon black. As a result, it was surprisingly found that the jet-blackness of the obtained resin composition is remarkably improved as compared with a resin composition containing no carbon diffusing agent but only carbon black. Preferably, the resin composition of this embodiment satisfies the relationships of the following formulas (1) and (2). Incidentally, L * values herein, a * value, and b * values refers to CIE LAB (L * a * b *) colorimetric L * value in the system, a * value, and b * values.
ΔL * ≦−0.3 (1)
Δb * ≦−0.15 (2)
[Delta] L *: the L * value of the resin composition, a value other than that it does not contain a light diffusing agent minus the L * value of the reference composition is the same composition as the resin composition [Delta] b *: the resin composition b * The value obtained by subtracting the b * value of the reference composition having the same composition as the resin composition except that the light diffusing agent is not included.
本実施形態の樹脂組成物は、好ましくは、ＣＩＥ ＬＡＢ（Ｌ＊ａ＊ｂ＊）表色系における、Ｌ＊値が１２．５０以下であり、かつ、ｂ＊値が０．７０以下である。なお、より好ましくは、Ｌ＊値１２．００以下であり、ｂ＊値は０．５０以下である。 The resin composition of the present embodiment preferably has an L * value of 12.50 or less and a b * value of 0.70 or less in the CIE LAB (L * a * b * ) color system. .. Note that, more preferably, the L * value is 12.00 or less and the b * value is 0.50 or less.
（熱可塑性樹脂）
本実施形態の樹脂組成物は、透明又は半透明の熱可塑性樹脂を含有する。熱可塑性樹脂の種類は特に限定されず、透明又は半透明であればよい。熱可塑性樹脂の具体例としては、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂；ポリスチレン、ＡＢＳ等のポリスチレン系樹脂；アクリル系樹脂；ポリカーボネート系樹脂；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；等を挙げることができる。なかでも、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂が好ましい。
(Thermoplastic resin)
The resin composition of the present embodiment contains a transparent or translucent thermoplastic resin. The type of thermoplastic resin is not particularly limited as long as it is transparent or translucent. Specific examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene; polystyrene resins such as polystyrene and ABS; acrylic resins; polycarbonate resins; polyester resins such as polyethylene terephthalate and polybutylene terephthalate. it can. Of these, polyolefin resins such as polyethylene and polypropylene are preferable.
（カーボンブラック）
カーボンブラックの種類は特に限定されない。カーボンブラックの具体例としては、ガスブラック、ファーネスブラック、ミディアムサーマルカーボンブラック、アセチレンブラック、ケッチェンブラック等を挙げることができる。
(Carbon black)
The type of carbon black is not particularly limited. Specific examples of carbon black include gas black, furnace black, medium thermal carbon black, acetylene black, and Ketjen black.
カーボンブラックは、粒径の小さいものを用いることが、より黒色度の高い樹脂組成物を得ることができるために好ましい。カーボンブラックの平均粒子径は、１０〜７０ｎｍであることが好ましい。なお、本明細書における「平均粒子径」は、動的光散乱法により測定される、体積基準の粒度分布における累積５０％となる粒子径（Ｄ５０）を意味する。 It is preferable to use carbon black having a small particle size because a resin composition having higher blackness can be obtained. The average particle size of carbon black is preferably 10 to 70 nm. Incidentally, the "average particle diameter" herein is measured by a dynamic light scattering method means a particle diameter (D 50) which is a 50% accumulation in volume-based particle size distribution.
樹脂組成物は、それ自体を成形して樹脂成形体とするもの、すなわち、樹脂成形体を成形する成形材料として用いることができる。樹脂組成物を成形材料として用いる場合、樹脂組成物中のカーボンブラックの含有量は、熱可塑性樹脂１００質量部に対して、０．０２５〜３質量部であることが好ましく、０．１〜２質量部であることがさらに好ましい。カーボンブラックの含有量を上記の範囲とすることで、黒色度がより高く、さらに漆黒性を向上させることができる。なお、カーボンブラックの含有量が、熱可塑性樹脂１００質量部に対して０．０２５質量部未満であると、薄肉部を有する成形体を製造した場合に着色効果がやや不足することがある。一方、カーボンブラックの含有量を、熱可塑性樹脂１００質量部に対して３質量部超としても、黒色度をさらに向上させることは困難になる傾向にある。 The resin composition can be used as a resin molded product by molding itself, that is, as a molding material for molding the resin molded product. When the resin composition is used as a molding material, the content of carbon black in the resin composition is preferably 0.025 to 3 parts by mass, and 0.1 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. More preferably, it is parts by mass. By setting the content of carbon black in the above range, the blackness is higher and the jet blackness can be further improved. When the content of carbon black is less than 0.025 parts by mass with respect to 100 parts by mass of the thermoplastic resin, the coloring effect may be slightly insufficient when a molded product having a thin portion is manufactured. On the other hand, even if the content of carbon black exceeds 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin, it tends to be difficult to further improve the blackness.
また、樹脂組成物は、カーボンブラック及び光拡散剤を高濃度に含有させることで、ベース樹脂を着色するための、いわゆるマスターバッチとして用いることができる。樹脂組成物をマスターバッチとして用いる場合、樹脂組成物中のカーボンブラックの含有量は、熱可塑性樹脂１００質量部に対して、１〜８０質量部であることが好ましく、１〜４０質量部であることがさらに好ましい。カーボンブラックの含有量を上記の範囲とすることで、黒色度がより高く、さらに漆黒性が向上した成形体を製造可能な樹脂組成物を提供しうるマスターバッチとすることができる。 Further, the resin composition can be used as a so-called masterbatch for coloring the base resin by containing carbon black and the light diffusing agent in a high concentration. When the resin composition is used as a masterbatch, the content of carbon black in the resin composition is preferably 1 to 80 parts by mass, and 1 to 40 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Is more preferable. By setting the content of carbon black within the above range, it is possible to provide a masterbatch that can provide a resin composition capable of producing a molded product having a higher blackness and further improving jetness.
（光拡散剤）
光拡散剤としては、樹脂材料等に配合される粉末状又は粒子状の一般的な光拡散剤を用いることができる。光拡散剤は、特定の屈折率を有するものであれば用いることができ、樹脂製の光拡散剤であってもよく、無機系の光拡散剤であってもよい。
(Light diffuser)
As the light diffusing agent, a general light diffusing agent in the form of powder or particles mixed with a resin material or the like can be used. Any light diffusing agent may be used as long as it has a specific refractive index, and may be a resin light diffusing agent or an inorganic light diffusing agent.
熱可塑性樹脂の屈折率ｎ１と光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）は、０を超えて０．１２未満であり、好ましくは０．０１〜０．０６、さらに好ましくは０．０２〜０．０５５である。｜ｎ１−ｎ２｜の値を上記の範囲内とすることで、青味で黒色度の高い、漆黒性に優れた樹脂組成物とすることができる。なお、本明細書における「屈折率」は、ＪＩＳ Ｋ ７１４２：２０１４に準拠して測定される、２５℃、ナトリウムＤ線（波長５８９ｎｍ）における屈折率を意味する。 Absolute value of the difference between the refractive index n 2 of the refractive index n 1 and the light diffusing agent of the thermoplastic resin (| n 1 -n 2 |) is less than 0.12 more than 0, preferably 0.01 to 0.06, and more preferably 0.02 to 0.055. By setting the value of |n 1 −n 2 | within the above range, it is possible to obtain a resin composition that is bluish, has a high degree of blackness, and is excellent in jet blackness. In addition, the "refractive index" in this specification means the refractive index in 25 degreeC and the sodium D line (wavelength 589 nm) measured based on JISK7142:2014.
光拡散剤の平均粒子径は０．３μｍ未満であり、好ましくは０．０１〜０．２５μｍ、さらに好ましくは０．０２〜０．２μｍである。その平均粒子径が０．３μｍ未満の光拡散剤を用いることで、青味で黒色度の高い、漆黒性に優れた樹脂組成物とすることができる。 The average particle size of the light diffusing agent is less than 0.3 μm, preferably 0.01 to 0.25 μm, and more preferably 0.02 to 0.2 μm. By using a light diffusing agent having an average particle diameter of less than 0.3 μm, it is possible to obtain a resin composition that is bluish, has a high degree of blackness, and is excellent in jet blackness.
樹脂組成物を成形材料として用いる場合、樹脂組成物中の光拡散剤の含有量は、熱可塑性樹脂１００質量部に対して、０．０２５〜１２質量部であることが好ましく、０．１〜８質量部であることがさらに好ましい。光拡散剤の含有量を上記の範囲とすることで、黒色度がより高く、さらに漆黒性を向上させることができる。なお、光拡散剤の含有量が、熱可塑性樹脂１００質量部に対して０．０２５質量部未満であると、薄肉部を有する成形体を製造した場合に、漆黒性の向上効果がやや不足することがある。一方、光拡散剤の含有量が、熱可塑性樹脂１００質量部に対して１２質量部超とすると、成形体がやや白ボケしやすくなる傾向にある。 When the resin composition is used as a molding material, the content of the light diffusing agent in the resin composition is preferably 0.025 to 12 parts by mass, and 0.1 to 100 parts by mass of the thermoplastic resin. It is more preferably 8 parts by mass. By setting the content of the light diffusing agent in the above range, the blackness is higher and the jet blackness can be further improved. When the content of the light diffusing agent is less than 0.025 parts by mass with respect to 100 parts by mass of the thermoplastic resin, the effect of improving jetness is slightly insufficient when a molded body having a thin portion is manufactured. Sometimes. On the other hand, when the content of the light diffusing agent is more than 12 parts by mass with respect to 100 parts by mass of the thermoplastic resin, the molded body tends to be slightly blurred.
樹脂組成物をマスターバッチとして用いる場合、樹脂組成物中の光拡散剤の含有量は、熱可塑性樹脂１００質量部に対して、１〜８０質量部であることが好ましく、１〜４０質量部であることがさらに好ましい。光拡散剤の含有量を上記の範囲とすることで、黒色度がより高く、さらに漆黒性が向上した成形体を製造可能な樹脂組成物を提供しうるマスターバッチとすることができる。 When the resin composition is used as a masterbatch, the content of the light diffusing agent in the resin composition is preferably 1 to 80 parts by mass, and 1 to 40 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is more preferable that there is. By setting the content of the light diffusing agent in the above range, it is possible to provide a masterbatch that can provide a resin composition capable of producing a molded product having higher blackness and further improving jetness.
（分散剤）
樹脂組成物には、カーボンブラックや光拡散剤を熱可塑性樹脂中に分散させるための分散剤を含有させることができる。分散剤としては、樹脂材料中に粉末又は粒子を分散させることが可能な一般的な分散剤を用いることができる。分散剤としては、例えば、金属石鹸、ワックス系の分散剤等を挙げることができる。
(Dispersant)
The resin composition may contain a dispersant for dispersing carbon black or a light diffusing agent in the thermoplastic resin. As the dispersant, a general dispersant capable of dispersing powder or particles in a resin material can be used. Examples of the dispersant include metal soap and wax-based dispersants.
（その他の成分）
樹脂組成物には、必要に応じて、上記の各成分以外の成分（その他の成分）をさらに含有させることができる。その他の成分としては、樹脂成形体を成形するための成形材料として用いられる通常の成分を挙げることができる。その他の成分としては、可塑剤、安定剤、酸化防止剤、紫外線吸収剤、紫外線安定剤、帯電防止材、難燃剤、防黴剤、滑剤、発泡剤、核剤、架橋剤、耐衝撃強化剤等を挙げることができる。
(Other ingredients)
If necessary, the resin composition may further contain components (other components) other than the above components. Examples of the other components include ordinary components used as a molding material for molding a resin molded body. Other components include plasticizers, stabilizers, antioxidants, UV absorbers, UV stabilizers, antistatic agents, flame retardants, mildew-proofing agents, lubricants, foaming agents, nucleating agents, cross-linking agents, impact strengthening agents. Etc. can be mentioned.
＜樹脂組成物の製造方法＞
本発明の一実施形態である樹脂組成物の製造方法は、透明又は半透明の熱可塑性樹脂、カーボンブラック、及び光拡散剤を含む原材料を混合して樹脂組成物を得る工程を有する。そして、前述の通り、その屈折率（ｎ２）が熱可塑性樹脂の屈折率（ｎ１）と異なる光拡散剤をカーボンブラックとともに熱可塑性樹脂に配合することで、光拡散剤を配合せずにカーボンブラックのみを配合したものに比して、漆黒性が向上した樹脂組成物を得ることができる。
<Method for producing resin composition>
A method for producing a resin composition, which is an embodiment of the present invention, includes a step of mixing a raw material containing a transparent or translucent thermoplastic resin, carbon black, and a light diffusing agent to obtain a resin composition. Then, as described above, by blending to the refractive index (n 2) thermoplastic resin is the refractive index of the thermoplastic resin and the different light diffusing agent (n 1) with carbon black, without compounding a light diffusing agent It is possible to obtain a resin composition having improved jet blackness as compared with a composition containing only carbon black.
（ｉ）熱可塑性樹脂の屈折率ｎ１と光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）を、０を超えて０．１２未満とすること；及び（ｉｉ）平均粒子径０．３μｍ未満の光拡散剤を用いること；以外は、いわゆる当業者に周知の方法によって各成分を混合する。これにより、漆黒性が向上した所望とする樹脂組成物を得ることができる。 (I) the absolute value of the difference between the refractive index n 2 of the refractive index n 1 and the light diffusing agent of the thermoplastic resin (| n 1 -n 2 |) and it is less than 0.12 and greater than 0; and ( ii) Using a light diffusing agent having an average particle size of less than 0.3 μm; except that the components are mixed by a method well known to those skilled in the art. Thereby, the desired resin composition having improved jetness can be obtained.
＜樹脂成形体＞
本発明の一実施形態である樹脂成形体は、前述の樹脂組成物の成形物である。本実施形態の樹脂成形体は、いわゆる当業者に周知の方法によって前述の樹脂組成物を所望とする形状に成形することで製造することができる。漆黒性に優れた樹脂組成物を成形した成形
物であることから、本実施形態の樹脂成形体も漆黒性に優れている。好適には、本実施形態の樹脂成形体のＣＩＥ ＬＡＢ（Ｌ＊ａ＊ｂ＊）表色系における、Ｌ＊値は１２．５０以下であり、かつ、ｂ＊値は０．７０以下である。
<Resin molding>
A resin molded body that is one embodiment of the present invention is a molded product of the above-mentioned resin composition. The resin molded body of the present embodiment can be manufactured by molding the resin composition into a desired shape by a method known to those skilled in the art. Since it is a molded product obtained by molding a resin composition having excellent jetness, the resin molded product of the present embodiment also has excellent jetness. Preferably, in the CIE LAB (L * a * b * ) color system of the resin molded product of the present embodiment, the L * value is 12.50 or less and the b * value is 0.70 or less. ..
また、樹脂組成物がカーボンブラックや光拡散剤を高濃度に含有する、いわゆるマスターバッチである場合には、カーボンブラック等が所望とする濃度となるような量の樹脂組成物（マスターバッチ）をベース樹脂に練り込んで成形材料を得る。そして、得られた成形材料を周知の方法によって所望とする形状に成形することで、漆黒性に優れた樹脂成形体とすることができる。 When the resin composition contains carbon black or a light diffusing agent in a high concentration, that is, a so-called masterbatch, an amount of the resin composition (masterbatch) such that carbon black has a desired concentration is prepared. A base material is kneaded to obtain a molding material. Then, by molding the obtained molding material into a desired shape by a known method, it is possible to obtain a resin molding having excellent jetness.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。 Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.
＜原料の準備＞
（樹脂）
表１に示す種類の樹脂１及び２を用意した。
<Preparation of raw materials>
(resin)
Resins 1 and 2 of the types shown in Table 1 were prepared.
（カーボンブラック）
表２に示す種類のカーボンブラック１〜３を用意した。
(Carbon black)
The types of carbon blacks 1 to 3 shown in Table 2 were prepared.
（光拡散剤）
表３に示す種類の光拡散剤１〜１８を用意した。
(Light diffuser)
Light diffusing agents 1 to 18 of the types shown in Table 3 were prepared.
（分散剤）
分散剤として金属石鹸（ジンクステアレート）を用意した。
(Dispersant)
A metal soap (zinc stearate) was prepared as a dispersant.
＜樹脂組成物の製造＞
（実施例１）
樹脂１ １００部、カーボンブラック１ ０．１部、光拡散剤１ ０．１部、及び分散剤０．２部をスーパーミキサーに入れて１分間混合して混合物を得た。３０ｍｍ押出機を使用し、加工温度２００℃の条件で得られた混合物を押出成形して、樹脂組成物の着色ペレットを得た。
<Production of resin composition>
(Example 1)
100 parts of Resin 1, 0.1 parts of Carbon Black 1, 0.1 parts of Light Diffusing Agent, and 0.2 parts of Dispersant were placed in a super mixer and mixed for 1 minute to obtain a mixture. The mixture obtained was extruded using a 30 mm extruder at a processing temperature of 200° C. to obtain colored pellets of the resin composition.
（実施例２〜１９、比較例１〜２７、参考例Ａ〜Ｇ）
表４及び５に示す種類及び量の各原料を用いたこと以外は、前述の実施例１と同様にして、樹脂組成物の着色ペレットを得た。
(Examples 2 to 19, Comparative Examples 1 to 27, Reference Examples A to G)
Colored pellets of the resin composition were obtained in the same manner as in Example 1 except that the raw materials of the types and amounts shown in Tables 4 and 5 were used.
＜評価＞
（成形体の製造）
５０ｔ射出成形機を使用し、加工温度２００℃、金型温度２５℃の条件で製造した各着色ペレットを射出成形して成形体を得た。
<Evaluation>
(Production of molded body)
Using a 50t injection molding machine, each colored pellet manufactured under the conditions of a processing temperature of 200°C and a mold temperature of 25°C was injection-molded to obtain a molded body.
（漆黒性及び漆黒性向上効果の評価）
得られた各成形体を１日間放置した。その後、コンピューターカラーマッチングにより、標準光源：Ｄ−６５、拡散照明：１０°の条件で各成形体のＬ＊値、ｂ＊値、及びａ＊値を測定した。測定したＬ＊値、ｂ＊値、及びａ＊値（いずれも絶対値）を表６及び７に示す。また、実施例及び比較例の各成形体のＬ＊値、ｂ＊値、及びａ＊値と、光拡散剤を含有しないこと以外は同一の組成の樹脂組成物で形成した参考例の成形体のＬ＊値、ｂ＊値、及びａ＊値との差（ΔＬ＊値、Δｂ＊値、及びΔａ＊値）を算出した。算出したΔＬ＊値、Δｂ＊値、及びΔａ＊値を表６及び７に示す。さらに、算出したΔＬ＊値、Δｂ＊値、及びΔａ＊値から、以下に示す評価基準にしたがって漆黒性向上効果を評価した。評価結果を表６及び７に示す。
(Evaluation of jet-blackness and jet-blackness improving effect)
Each of the obtained molded bodies was left for 1 day. Then, the L * value, b * value, and a * value of each molded product were measured by computer color matching under the conditions of standard light source: D-65 and diffused illumination: 10°. The measured L * value, b * value, and a * value (all are absolute values) are shown in Tables 6 and 7. Further, the L * value, the b * value, and the a * value of each of the molded products of Examples and Comparative Examples, and the molded product of Reference Example formed from the resin composition having the same composition except that the light diffusing agent is not contained. Of L * value, b * value, and a * value (ΔL * value, Δb * value, and Δa * value) were calculated. The calculated ΔL * value, Δb * value, and Δa * value are shown in Tables 6 and 7. Furthermore, the effect of improving jetness was evaluated from the calculated ΔL * value, Δb * value, and Δa * value according to the following evaluation criteria. The evaluation results are shown in Tables 6 and 7.
［ΔＬ＊値］
◎：−１．０以下
○：−１．０を超えて、−０．３以下
△：−０．３を超えて、０．０未満
×：０．０以上
［Δｂ＊値］
◎：−０．３以下
○：−０．３を超えて、−０．１５以下
△：−０．１５を超えて０．０未満
×：０．０以上
[ΔL * value]
⊚: −1.0 or less O: −1.0 or more and −0.3 or less Δ: −0.3 or more and less than 0.0 x: 0.0 or more [Δb * value]
⊚: −0.3 or less O: −0.3 or more and −0.15 or less Δ: −0.15 or more and less than 0.0 x: 0.0 or more
本発明の樹脂組成物は、漆黒性に優れた樹脂成形体を製造するための原料として有用である。
The resin composition of the present invention is useful as a raw material for producing a resin molded product having excellent jetness.
Claims (8)
前記熱可塑性樹脂の屈折率ｎ１と前記光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）が、０を超えて０．１２未満であり、
前記光拡散剤の平均粒子径が、０．３μｍ未満である樹脂組成物。 Contains a transparent or translucent thermoplastic resin, carbon black, and a light diffusing agent,
The absolute value (|n 1 −n 2 |) of the difference between the refractive index n 1 of the thermoplastic resin and the refractive index n 2 of the light diffusing agent is more than 0 and less than 0.12.
A resin composition in which the average particle diameter of the light diffusing agent is less than 0.3 μm.
ΔＬ＊≦−０．３ ・・・（１）
Δｂ＊≦−０．１５ ・・・（２）
ΔＬ＊：樹脂組成物のＬ＊値から、前記光拡散剤を含有しないこと以外は前記樹脂組成物と同一の組成である基準組成物のＬ＊値を減じた値
Δｂ＊：樹脂組成物のｂ＊値から、前記光拡散剤を含有しないこと以外は前記樹脂組成物と同一の組成である基準組成物のｂ＊値を減じた値 The resin composition according to claim 1, which satisfies the relationships of the following formulas (1) and (2).
ΔL * ≦−0.3 (1)
Δb * ≦−0.15 (2)
[Delta] L *: the L * value of the resin composition, a value obtained by subtracting the L * value of the reference composition except that it does not contain the same composition as the resin composition of the light diffusing agent [Delta] b *: the resin composition from the b * value, the value except that it does not contain the light diffusing agent obtained by subtracting the b * value of the reference composition is a composition identical to the resin composition
前記光拡散剤の含有量が、前記熱可塑性樹脂１００質量部に対して、０．０２５〜１２質量部である請求項３に記載の樹脂組成物。 The content of the carbon black is 0.025 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin,
The resin composition according to claim 3, wherein the content of the light diffusing agent is 0.025 to 12 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
前記光拡散剤の含有量が、前記熱可塑性樹脂１００質量部に対して、１〜８０質量部である請求項５に記載の樹脂組成物。 The content of the carbon black is 1 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic resin,
The resin composition according to claim 5, wherein the content of the light diffusing agent is 1 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
前記熱可塑性樹脂の屈折率ｎ１と前記光拡散剤の屈折率ｎ２の差の絶対値（｜ｎ１−ｎ２｜）が、０を超えて０．１２未満であり、
前記光拡散剤の平均粒子径が、０．３μｍ未満である、漆黒性が向上した樹脂組成物の製造方法。
There is a step of mixing a transparent or translucent thermoplastic resin, carbon black, and raw materials containing a light diffusing agent to obtain a resin composition,
The absolute value (|n 1 −n 2 |) of the difference between the refractive index n 1 of the thermoplastic resin and the refractive index n 2 of the light diffusing agent is more than 0 and less than 0.12.
A method for producing a resin composition having improved jet blackness, wherein the light diffusing agent has an average particle size of less than 0.3 μm.
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