JP2012082380A - Expandable polystyrene-based colored resin particle and method for producing the same, colored resin pre-expanded particle, and colored resin expansion molded body and application of the same - Google Patents
Expandable polystyrene-based colored resin particle and method for producing the same, colored resin pre-expanded particle, and colored resin expansion molded body and application of the same Download PDFInfo
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Abstract
Description
本発明は、発泡剤を含み、着色されたポリスチレン系樹脂粒子からなる発泡性ポリスチレン系着色樹脂粒子とその製造方法に関し、特に、色むらが無く、一様に着色したポリスチレン系着色樹脂発泡成形体を容易に製造することができる発泡性ポリスチレン系着色樹脂粒子とその製造方法、該着色樹脂粒子を発泡させた着色樹脂予備発泡粒子、該着色樹脂予備発泡粒子を型内発泡成形して得られた着色樹脂発泡成形体とその用途に関する。 TECHNICAL FIELD The present invention relates to an expandable polystyrene-based colored resin particle comprising a foaming agent and comprising colored polystyrene-based resin particles and a method for producing the same, and in particular, a polystyrene-based colored resin foamed molded article that is uniformly colored without color unevenness. Expandable polystyrene-based colored resin particles that can be easily produced, a method for producing the same, a colored resin pre-foamed particle obtained by foaming the colored resin particle, and obtained by foam-molding the colored resin pre-foamed particle The present invention relates to a colored resin foam molding and its use.
ポリスチレン系樹脂の発泡成形体は、運搬用容器や、包装用容器として広く利用されている。そのうち、鮮魚用や建材用途などでは他容器と区別する目的や、意匠性を高める為に着色して使用されている。 Polystyrene resin foam moldings are widely used as transport containers and packaging containers. Among them, for fresh fish and building materials, it is used for coloring purposes in order to distinguish it from other containers and to improve design.
例えば、鮮魚用ではブルー、パープル、建材用途ではオレンジ、グリーン等に着色された発泡成形体を使用する。一方、グレー色に着色しておくと、汚れが目立たないという利点があるので、構造部材として使用する用途にはグレー色に着色されることが多い。グレー色に着色された発泡性粒子を作るには、着色剤としてこれまでカーボンブラックが用いられるのが一般的であった。 For example, a foamed molded product colored in blue or purple for fresh fish and orange or green for building materials is used. On the other hand, since it has the advantage that dirt is not conspicuous if it is colored in gray, it is often colored in gray for use as a structural member. In order to produce expandable particles colored in gray, carbon black has been generally used as a colorant.
しかしカーボンブラックを含んだ発泡性粒子を作るには、ポリスチレン系樹脂の重合段階で添加する必要があり、発泡剤を含浸させるときに粒子にカーボンブラックを吸収させることができず製造工程が煩雑になる。 However, in order to make expandable particles containing carbon black, it is necessary to add it at the polymerization stage of polystyrene resin, and when impregnating with a foaming agent, the particles cannot absorb carbon black and the manufacturing process is complicated. Become.
一般に、着色された発泡性樹脂粒子を作るには、幾つかの方法が知られている。
例えば、特許文献１（特公平６−１０２７０号公報）、特許文献２（特公平６−２３２６６号公報）にあるように、発泡剤の添加過程で染料を添加する方法が知られている。
In general, several methods are known for producing colored expandable resin particles.
For example, as disclosed in Patent Document 1 (Japanese Patent Publication No. 6-10270) and Patent Document 2 (Japanese Patent Publication No. 6-23266), a method of adding a dye in the process of adding a foaming agent is known.
また、上述の方法において染料又は顔料の離脱を防止するために、被覆剤を用いて染料又は顔料を樹脂粒子表面に被覆する方法があるが、この方法では内部までむらなく着色することができないだけでなく、被覆工程が余分に必要なために製造工程が複雑になるという欠点があった。これら従来処方に使用される染料は、親油性の強いものが使用されている。 In addition, in order to prevent the dye or pigment from detaching in the above-described method, there is a method of coating the surface of the resin particle with the dye or pigment using a coating agent. In addition, the manufacturing process is complicated because an extra coating process is required. As dyes used in these conventional formulations, those having strong lipophilicity are used.
しかし、従来の方法では、発泡性ポリスチレン系樹脂粒子への着色にムラが生じ易くなる傾向にあった。
特に、２種以上の染料を混合して使用する場合に着色むらが生じ易く、着色した発泡性ポリスチレン系着色樹脂粒子を用いて製造した発泡成形体は、外観に劣るものとなりやすかった。
However, the conventional method tends to cause unevenness in coloring the expandable polystyrene resin particles.
In particular, when two or more kinds of dyes are mixed and used, uneven coloring tends to occur, and a foamed molded article produced using colored expandable polystyrene-based colored resin particles tends to be inferior in appearance.
本発明は、前記事情に鑑みてなされ、色むらが無く、一様に着色したポリスチレン系着色樹脂発泡成形体を容易に製造することができる発泡性ポリスチレン系着色樹脂粒子とその製造方法の提供を課題とする。 The present invention has been made in view of the above circumstances, and provides an expandable polystyrene-based colored resin particle capable of easily producing a uniformly colored polystyrene-based colored resin foamed molded article without color unevenness and a method for producing the same. Let it be an issue.
発明者らは、ブルーに着色する場合や、２種以上併用してグレーに着色する場合にアセトアニリド基を有する染料を使用した場合や、更に、従来のアントラキノン系染料と併用しても色むらが生じ難いことを見出し、均一に染色できることを見出した。 The inventors have colored unevenness even when using a dye having an acetanilide group in the case of coloring in blue, in the case of using two or more kinds in combination and coloring in gray, and even in combination with a conventional anthraquinone dye. It was found that it was difficult to occur, and it was found that it can be uniformly dyed.
本発明は、染料で着色された発泡性ポリスチレン系着色樹脂粒子において、アセトアニリド基含有染料を含有することを特徴とする発泡性ポリスチレン系着色樹脂粒子を提供する。 The present invention provides an expandable polystyrene-based colored resin particle characterized by containing an acetanilide group-containing dye in an expandable polystyrene-based colored resin particle colored with a dye.
本発明の発泡性ポリスチレン系着色樹脂粒子において、前記アセトアニリド基含有染料が、ＤｉｓｐｅｒｓｅＢｌｕｅ１６５、ＤｉｓｐｅｒｓｅＢｌｕｅ７９、ＤｉｓｐｅｒｓｅＲｅｄ８２、ＤｉｓｐｅｒｓｅＲｅｄ１５２、ＤｉｓｐｅｒｓｅＲｅｄ１６７、ＤｉｓｐｅｒｓｅＲｅｄ２７７、ＤｉｓｐｅｒｓｅＹｅｌｌｏｗ３からなる群から選択される１種又は２種以上であることが好ましい。 In the expandable polystyrene-based colored resin particles of the present invention, the acetanilide group-containing dye is selected from the group consisting of DisperseBlue165, DisperseBlue79, DisperseRed82, DisperseRed152, DisperseRed167, DispersedRed277, DisperseYellow3, or one or more preferable species selected from the group consisting of two or more. .
本発明の発泡性ポリスチレン系着色樹脂粒子において、前記アセトアニリド基含有染料とアントラキノン系染料とを含有する構成としてもよい。 The expandable polystyrene-based colored resin particles of the present invention may be configured to contain the acetanilide group-containing dye and an anthraquinone dye.
本発明の発泡性ポリスチレン系着色樹脂粒子において、発泡性ポリスチレン系着色樹脂粒子中にポリエチレン系樹脂が含有されている構成としてもよい。 The expandable polystyrene-based colored resin particles of the present invention may have a configuration in which a polyethylene-based resin is contained in the expandable polystyrene-based colored resin particles.
また本発明は、ポリスチレン系樹脂粒子を耐圧密閉型の混合機に入れ、撹拌しながら６０℃以上に加熱し、揮発性発泡剤を液状で耐圧密閉型混合機に圧入して揮発性発泡剤をポリスチレン系樹脂粒子に吸収させて発泡性ポリスチレン系樹脂粒子を製造する方法において、アセトアニリド基含有染料を界面活性剤と水系媒体に予め分散させた後に添加して発泡性ポリスチレン系着色樹脂粒子を得ることを特徴とする発泡性ポリスチレン系着色樹脂粒子の製造方法を提供する。 In the present invention, the polystyrene resin particles are placed in a pressure-resistant sealed mixer, heated to 60 ° C. or higher with stirring, and the volatile foaming agent is pressed into a pressure-resistant sealed mixer to form a volatile foaming agent. In the method of producing expandable polystyrene resin particles by absorbing them in polystyrene resin particles, an acetanilide group-containing dye is dispersed in advance in a surfactant and an aqueous medium and then added to obtain expandable polystyrene colored resin particles. A method for producing expandable polystyrene-based colored resin particles is provided.
本発明の発泡性ポリスチレン系着色樹脂粒子の製造方法において、前記アセトアニリド基含有系染料が、ＤｉｓｐｅｒｓｅＢｌｕｅ１６５、ＤｉｓｐｅｒｓｅＢｌｕｅ７９、ＤｉｓｐｅｒｓｅＲｅｄ８２、ＤｉｓｐｅｒｓｅＲｅｄ１５２、ＤｉｓｐｅｒｓｅＲｅｄ１６７、ＤｉｓｐｅｒｓｅＲｅｄ２７７、ＤｉｓｐｅｒｓｅＹｅｌｌｏｗ３からなる群から選択される１種又は２種以上であることが好ましい。 In the method for producing expandable polystyrene colored resin particles of the present invention, the acetanilide group-containing dye is selected from the group consisting of DisperseBlue165, DisperseBlue79, DispersedRed82, DispersedRed152, DispersedRed167, DispersedRed277, DisperseYellow3, or a species selected from two or more. Preferably there is.
本発明の発泡性ポリスチレン系着色樹脂粒子の製造方法において、前記アセトアニリド基含有染料とアントラキノン系染料とを併用して添加する構成としてもよい。 In the method for producing expandable polystyrene-based colored resin particles of the present invention, the acetanilide group-containing dye and the anthraquinone dye may be used in combination.
本発明の発泡性ポリスチレン系着色樹脂粒子の製造方法において、前記発泡性ポリスチレン系樹脂粒子中にポリエチレン系樹脂が含有されている構成としてもよい。 In the method for producing expandable polystyrene colored resin particles of the present invention, the expandable polystyrene resin particles may include a polyethylene resin.
また本発明は、前記発泡性ポリスチレン系着色樹脂粒子を加熱し予備発泡させて得られた着色樹脂予備発泡粒子を提供する。 The present invention also provides colored resin pre-expanded particles obtained by heating and pre-expanding the expandable colored polystyrene resin particles.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた着色樹脂発泡成形体を提供する。 The present invention also provides a colored resin foam molded article obtained by in-mold foam molding of the colored resin pre-expanded particles.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた建材用断熱材を提供する。 Moreover, this invention provides the heat insulating material for building materials obtained by carrying out in-mold foam molding of the said colored resin pre-expanded particle.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた食品容器を提供する。 The present invention also provides a food container obtained by in-mold foam molding of the colored resin pre-expanded particles.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた搬送容器を提供する。 The present invention also provides a transport container obtained by in-mold foam molding of the colored resin pre-expanded particles.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた保冷断熱容器を提供する。 The present invention also provides a cold insulated container obtained by in-mold foam molding of the colored resin pre-expanded particles.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた装飾ブロックを提供する。 The present invention also provides a decorative block obtained by in-mold foam molding of the colored resin pre-expanded particles.
また本発明は、前記着色樹脂予備発泡粒子を型内発泡成形して得られた土木用ブロックを提供する。 The present invention also provides a civil engineering block obtained by in-mold foam molding of the colored resin pre-expanded particles.
本発明の発泡性ポリスチレン系着色樹脂粒子は、染料としてアセトアニリド基含有染料を含有するものなので、色むらが無く、一様に着色した着色樹脂発泡成形体を容易に製造することができる。
また、アセトアニリド基含有染料は、異なる色の染料を複数種組み合わせてポリスチレン系樹脂粒子の表面に含浸させることで、目的の混色を美麗かつ均一に着色できることから、着色のバリエーションを増やすことができる。
Since the expandable polystyrene-based colored resin particles of the present invention contain an acetanilide group-containing dye as a dye, a uniformly colored colored resin foam molded article can be easily produced without color unevenness.
In addition, the acetanilide group-containing dye can be colored beautifully and uniformly by impregnating the surface of the polystyrene-based resin particles with a combination of a plurality of dyes of different colors, and therefore, variations in coloring can be increased.
本発明の発泡性ポリスチレン系着色樹脂粒子は、染料で着色された発泡性ポリスチレン系着色樹脂粒子において、アセトアニリド基含有染料を含有することを特徴としている。 The expandable polystyrene-based colored resin particles of the present invention are characterized in that the expandable polystyrene-based colored resin particles colored with a dye contain an acetanilide group-containing dye.
本発明の発泡性ポリスチレン系着色樹脂粒子に用いられるポリスチレン系樹脂粒子としては、例えば、次の（１）〜（３）の製造方法で得られたポリスチレン系樹脂粒子を使用できる。
（１）水系懸濁液中にスチレン系単量体を主成分とする重合性単量体を分散させ重合を行い、ポリスチレン系樹脂粒子を得る、いわゆる懸濁重合法、
（２）水系懸濁液中にポリスチレン系樹脂種粒子を分散させた後に、スチレン系単量体を主成分とする重合性単量体を該種粒子に吸収させて重合を行い、ポリスチレン系樹脂粒子を得る、いわゆるシード重合法、
（３）押出機にポリスチレン系樹脂を投入して加熱溶融し、押出機吐出側に取り付けた多数の小孔を有するダイの該小孔から発泡剤混合樹脂を押し出し、その直後に水中で切断し、急冷することでポリスチレン系樹脂粒子を得る、いわゆる溶融押出法（水中カット法などとも称される）。
As the polystyrene resin particles used for the expandable polystyrene colored resin particles of the present invention, for example, polystyrene resin particles obtained by the following production methods (1) to (3) can be used.
(1) A so-called suspension polymerization method in which a polymerizable monomer having a styrene monomer as a main component is dispersed in an aqueous suspension to perform polymerization to obtain polystyrene resin particles.
(2) After the polystyrene resin seed particles are dispersed in the aqueous suspension, the polymerizable monomer mainly containing a styrene monomer is absorbed into the seed particles to perform polymerization, and the polystyrene resin So-called seed polymerization method to obtain particles,
(3) A polystyrene resin is put into an extruder and melted by heating. The foaming agent mixed resin is extruded from the small holes of a die having a large number of small holes attached to the discharge side of the extruder, and immediately after that, cut in water. A so-called melt-extrusion method (also referred to as an underwater cutting method) that obtains polystyrene-based resin particles by rapid cooling.
前記（１）懸濁重合法及び（２）シード重合法で用いるスチレン系単量体としては、スチレン、α−メチルスチレン、ビニルトルエン、クロロスチレン、エチルスチレン、ｉ−プロピルスチレン、ジメチルスチレン、ブロモスチレン等のスチレン系単量体を主成分とし、スチレン系単量体を通常、５０質量％以上、好ましくは８０質量％以上含む。これらのスチレン系単量体の中でも、スチレンが特に好ましい。
更にスチレン系単量体に併用可能な重合性単量体としては、スチレン系単量体と共重合可能なものであれば特に限定されず、ジビニルベンゼン、アルキレングリコールジメタクリレート、アクリロニトリル、メチルメタクリレート等が挙げられる。
Examples of the styrene monomer used in the above (1) suspension polymerization method and (2) seed polymerization method include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, bromo. The main component is a styrene monomer such as styrene, and the styrene monomer is usually contained in an amount of 50% by mass or more, preferably 80% by mass or more. Of these styrene monomers, styrene is particularly preferable.
Further, the polymerizable monomer that can be used in combination with the styrene monomer is not particularly limited as long as it is copolymerizable with the styrene monomer, and divinylbenzene, alkylene glycol dimethacrylate, acrylonitrile, methyl methacrylate, and the like. Is mentioned.
また（２）シード重合法で発泡性ポリスチレン系樹脂粒子を製造する場合、前記懸濁重合法により得られるポリスチレン系樹脂粒子を種粒子として使用したり、ポリスチレン系樹脂を押出機によりあらかじめ所望の粒子径に調整した後、種粒子として使用しても良い。
（２）シード重合法において押出機を用いて種粒子を作製する場合、或いは（３）溶融押出法において使用するポリスチレン系樹脂は、市販されている通常のポリスチレン系樹脂、懸濁重合法などの方法で新たに作製したポリスチレン系樹脂などの、リサイクル原料でないポリスチレン系樹脂（バージンポリスチレン）を使用できる他、使用済みのポリスチレン系樹脂発泡成形体を再生処理して得られたリサイクル原料を使用することができる。このリサイクル原料としては、使用済みのポリスチレン系樹脂発泡成形体、例えば、魚箱、家電緩衝材、食品包装用トレーなどを回収し、リモネン溶解方式や加熱減容方式によって再生したリサイクル原料などが挙げられる。
(2) When producing expandable polystyrene resin particles by the seed polymerization method, the polystyrene resin particles obtained by the suspension polymerization method are used as seed particles, or the polystyrene resin is obtained in advance by an extruder. After adjusting to the diameter, it may be used as seed particles.
(2) When seed particles are produced using an extruder in the seed polymerization method, or (3) polystyrene resins used in the melt extrusion method are commercially available ordinary polystyrene resins, suspension polymerization methods, etc. In addition to using polystyrene resins that are not recycled materials (virgin polystyrene), such as newly produced polystyrene resins by the method, use recycled materials obtained by reprocessing used polystyrene resin foam moldings. Can do. Examples of this recycled material include recycled polystyrene resin foam molded products such as fish boxes, household appliance cushioning materials, food packaging trays, etc., and recycled by the limonene dissolution method or heating volume reduction method. It is done.
前記発泡性ポリスチレン系樹脂粒子の粒子径は、特に限定されないが、成形時の成形型キャビティ内への予備発泡粒子の充填性等から、通常、０．３〜２．０ｍｍ程度であり、０．３〜１．４ｍｍが好ましい。 The particle diameter of the expandable polystyrene resin particles is not particularly limited, but is usually about 0.3 to 2.0 mm from the viewpoint of filling of the pre-expanded particles into the mold cavity at the time of molding. 3-1.4 mm is preferable.
本発明において、使用するポリスチレン系樹脂の分子量は、ＧＰＣ法による質量平均分子量（Ｍｗ）が１７万〜７０万であるのが好ましい。ポリスチレン系樹脂の分子量が１７万を下回ると、最終的に得られる発泡成形体の強度が低下し、また７０万を上回ると充分な発泡性が得られ難くなるので好ましくない。 In the present invention, the molecular weight of the polystyrene-based resin used is preferably 170,000 to 700,000 in terms of mass average molecular weight (Mw) by GPC method. If the molecular weight of the polystyrene-based resin is less than 170,000, the strength of the foamed molded product finally obtained is lowered, and if it exceeds 700,000, it is difficult to obtain sufficient foamability, which is not preferable.
前記（１）懸濁重合法および（２）シード重合法で使用する重合開始剤としては、通常、スチレンの懸濁重合において用いられるものであれば特に限定されず、例えばラジカル発生型重合開始剤を用いることができる。具体的には、ベンゾイルパーオキサイド、ラウリルパーオキサイド、ｔ−ブチルパーオキサイド、ｔ−ブチルパーオキシピバレート、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシアセテート、２，２−ｔ−ブチルパーオキシブタン、ｔ−ブチルパーオキシ−３，３，５−トリメチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート等の有機過酸化物やアゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル等のアゾ化合物が挙げられる。これらの重合開始剤は単独で、または２種以上を組合わせて用いることができる。 The polymerization initiator used in the above (1) suspension polymerization method and (2) seed polymerization method is not particularly limited as long as it is usually used in suspension polymerization of styrene. For example, a radical generating polymerization initiator is used. Can be used. Specifically, benzoyl peroxide, lauryl peroxide, t-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-t-butylperoxide Organic peroxides such as oxybutane, t-butylperoxy-3,3,5-trimethylhexanoate, di-t-butylperoxyhexahydroterephthalate, azobisisobutyronitrile, azobisdimethylvaleronitrile, etc. Of the azo compound. These polymerization initiators can be used alone or in combination of two or more.
前記の重合において、ポリスチレン系樹脂粒子中に残留するスチレン系単量体を低減するために、高温分解型の重合開始剤を使用し、最終の重合温度を１１５℃以上に設定するのが好ましい。高温分解型の重合開始剤としては、例えばｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシピバレート、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシアセテート、２，２−ｔ−ブチルパーオキシブタンなどの半減期１０時間を得るための温度が１００〜１１５℃のものが挙げられる。なお、高温分解型の重合開始剤を過剰に加えると分解副生成物であるアルコール類が発生するので好ましくない。 また、前記の重合において、ポリスチレン系樹脂粒子の分子量を調整し、単量体の残留量を減少させるという点で、１０時間の半減期を得るための分解温度が８０〜１２０℃の範囲にある重合開始剤を２種以上組合わせて用いるのが好ましい。 In the polymerization described above, in order to reduce the styrene monomer remaining in the polystyrene resin particles, it is preferable to use a high temperature decomposition type polymerization initiator and set the final polymerization temperature to 115 ° C. or higher. Examples of the high-temperature decomposition type polymerization initiator include t-butyl peroxybenzoate, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-t-butyl peroxy. Examples include butane having a temperature of 100 to 115 ° C. for obtaining a half-life of 10 hours. An excessive addition of a high temperature decomposition type polymerization initiator is not preferable because alcohols as decomposition byproducts are generated. In the polymerization, the decomposition temperature for obtaining a half-life of 10 hours is in the range of 80 to 120 ° C. in terms of adjusting the molecular weight of the polystyrene resin particles and reducing the residual amount of monomer. It is preferable to use a combination of two or more polymerization initiators.
前記（１）懸濁重合または（２）シード重合を行う際に、スチレン系単量体の小滴または種粒子を水性媒体中に分散させるために、懸濁剤を用いてもよい。懸濁剤としては、例えばポリビニルアルコール、メチルセルロース、ポリアクリルアミド、ポリビニルピロリドン等の水溶性高分子や、第三リン酸カルシウム、ピロリン酸マグネシウム等の難水溶性無機化合物等が挙げられる。なお、難水溶性無機化合物を用いる場合にはアニオン界面活性剤を併用するのが好ましい。 前記アニオン界面活性剤としては、例えば脂肪酸石鹸、Ｎ−アシルアミノ酸またはその塩、アルキルエーテルカルボン酸塩等のカルボン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸エステル塩、アルキルスルホ酢酸塩、α−オレフィンスルホン酸塩等のスルホン酸塩；高級アルコール硫酸エステル塩、第二級高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩等の硫酸エステル塩；アルキルエーテルリン酸エステル塩、アルキルリン酸エステル塩等のリン酸エステル塩などが挙げられる。前記のようにして得られるポリスチレン系樹脂粒子に、懸濁重合含浸法あるいは後含浸法によって発泡剤および可塑剤を含浸させることにより、発泡性ポリスチレン系樹脂粒子を製造することができる。 In carrying out the (1) suspension polymerization or (2) seed polymerization, a suspending agent may be used to disperse styrene monomer droplets or seed particles in an aqueous medium. Examples of the suspending agent include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyacrylamide, and polyvinyl pyrrolidone, and poorly water-soluble inorganic compounds such as tricalcium phosphate and magnesium pyrophosphate. In addition, when using a slightly water-soluble inorganic compound, it is preferable to use an anionic surfactant together. Examples of the anionic surfactant include fatty acid soaps, N-acyl amino acids or salts thereof, carboxylates such as alkyl ether carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates, alkylsulfates. Sulfates such as acetates and α-olefin sulfonates; sulfates such as higher alcohol sulfates, secondary higher alcohol sulfates, alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates; alkyls And phosphoric acid ester salts such as ether phosphoric acid ester salts and alkyl phosphoric acid ester salts. Expandable polystyrene resin particles can be produced by impregnating the polystyrene resin particles obtained as described above with a foaming agent and a plasticizer by a suspension polymerization impregnation method or a post-impregnation method.
本発明の発泡性ポリスチレン系着色樹脂粒子に用いられるアセトアニリド基含有染料としては、分子内にアセトアニリド基を有している染料化合物であればよく、特に限定されない。本発明の特に好ましい実施形態において、アセトアニリド基含有染料としては、ＤｉｓｐｅｒｓｅＢｌｕｅ１６５、ＤｉｓｐｅｒｓｅＢｌｕｅ７９、ＤｉｓｐｅｒｓｅＲｅｄ８２、ＤｉｓｐｅｒｓｅＲｅｄ１５２、ＤｉｓｐｅｒｓｅＲｅｄ１６７、ＤｉｓｐｅｒｓｅＲｅｄ２７７、ＤｉｓｐｅｒｓｅＹｅｌｌｏｗ３からなる群から選択される１種又は２種以上が挙げられる。 The acetanilide group-containing dye used for the expandable polystyrene-based colored resin particles of the present invention is not particularly limited as long as it is a dye compound having an acetanilide group in the molecule. In a particularly preferred embodiment of the present invention, the acetanilide group-containing dye includes one or more selected from the group consisting of DisperseBlue165, DisperseBlue79, DisperseRed82, DisperseRed152, DisperseRed167, DisperseRed277, DisperseYellow3.
本発明の発泡性ポリスチレン系着色樹脂粒子において、前記アセトアニリド基含有染料の含有量は、０．００３〜０．４０質量％の範囲内であることが好ましく、０．００５〜０．４０質量％の範囲内であることがより好ましく、０．０２〜０．４０質量％がさらに好ましく、０．０４〜０．３０質量％が最も好ましい。アセトアニリド基含有染料の含有量が前記範囲未満であると、最終的に得られる発泡成形体の着色度合が弱くなってしまう。一方、アセトアニリド系染料の含有量が前記範囲を超えると、コスト高となるばかりか、成形性が低下するために好ましくない。 In the expandable polystyrene-based colored resin particles of the present invention, the content of the acetanilide group-containing dye is preferably in the range of 0.003 to 0.40% by mass, and 0.005 to 0.40% by mass. It is more preferable to be within the range, 0.02 to 0.40% by mass is further preferable, and 0.04 to 0.30% by mass is most preferable. When the content of the acetanilide group-containing dye is less than the above range, the degree of coloration of the finally obtained foamed molded product becomes weak. On the other hand, if the content of the acetanilide dye exceeds the above range, it is not preferable because not only the cost increases but also the moldability decreases.
本発明の発泡性ポリスチレン系着色樹脂粒子において、色の異なる２種類以上のアセトアニリド基含有染料又はアセトアニリド基含有染料と別種の染料とを含有させることによって、所望の混色に着色することもできる。混色を得るための染料の種類や組み合わせは特に限定されない。 The expandable polystyrene-based colored resin particles of the present invention can be colored in a desired color mixture by containing two or more different acetanilide group-containing dyes or acetanilide group-containing dyes and different dyes. The kind and combination of the dyes for obtaining the color mixture are not particularly limited.
アセトアニリド系染料に他の染料を組み合わせる場合、他の染料としては、例えば、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１６７、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１１４、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１６３、ＳｏｌｖｅｎｔＹｅｌｌｏｗ９３、ＳｏｌｖｅｎｔＹｅｌｌｏｗ３３、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１６、ＳｏｌｖｅｎｔＧｒｅｅｎ５、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１０４、ＳｏｌｖｅｎｔＯｒａｎｇｅ６０、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１４、ＳｏｌｖｅｎｔＯｒａｎｇｅ６３、ＶａｔＲｅｄ４１、ＳｏｌｖｅｎｔＲｅｄ１４９、ＳｏｌｖｅｎｔＲｅｄ１１１、ＳｏｌｖｅｎｔＲｅｄ１３５、ＳｏｌｖｅｎｔＲｅｄ１７９、ＳｏｌｖｅｎｔＲｅｄ１４６、ＳｏｌｖｅｎｔＲｅｄ２２、ＳｏｌｖｅｎｔＲｅｄ５２、ＳｏｌｖｅｎｔＶｉｏｌｅｔ３１、ＳｏｌｖｅｎｔＶｉｏｌｅｔ１３、ＳｏｌｖｅｎｔＢｌｕｅ３５、ＳｏｌｖｅｎｔＢｌｕｅ３６、ＳｏｌｖｅｎｔＢｌｕｅ９７、ＳｏｌｖｅｎｔＢｌｕｅ８７、ＳｏｌｖｅｎｔＧｒｅｅｎ３、ＰｉｇｍｅｎｔＲｅｄ１７０等が挙げられる。 When combining other dye acetanilide dye, other dyes, for example, SolventYellow167, SolventYellow114, SolventYellow163, SolventYellow93, SolventYellow33, SolventYellow16, SolventGreen5, SolventYellow104, SolventOrange60, SolventYellow14, SolventOrange63, VatRed41, SolventRed149, SolventRed111, SolventRed135, SolventRed179 , SolventRed146, SolventRed22, SolventRed52, SolventViole 31, SolventViolet13, SolventBlue35, SolventBlue36, SolventBlue97, SolventBlue87, SolventGreen3, PigmentRed170 and the like.
本発明の発泡性ポリスチレン系着色樹脂粒子に用いられる発泡剤としては、一般の熱可塑性樹脂発泡体の製造に用いられている炭素数５以下の脂肪族炭化水素、例えばｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン、ネオペンタン等が挙げられる。 Examples of the foaming agent used in the expandable polystyrene-based colored resin particles of the present invention include aliphatic hydrocarbons having 5 or less carbon atoms used for the production of general thermoplastic resin foams, such as n-butane, isobutane, n -Pentane, isopentane, neopentane and the like.
前記発泡剤の含有割合は、ポリスチレン系樹脂粒子に対して３〜１０質量％の範囲が好ましく、４〜９質量％がより好ましく、５〜９質量％がさらに好ましく、５〜８質量％が最も好ましい。前記含有割合が３質量％を下回ると、低密度化が困難であるばかりでなく、成形時の二次発泡力を高める効果が得られないために発泡成形体の外観が劣るようになる。また、含有割合が１０質量％を上回ると、発泡成形時の収縮、予備発泡粒子中の残存ガスの調整時間の遅延、かつ成形サイクルが長くなり、生産性の点から好ましくない。 The content of the foaming agent is preferably in the range of 3 to 10% by mass, more preferably 4 to 9% by mass, further preferably 5 to 9% by mass, and most preferably 5 to 8% by mass with respect to the polystyrene resin particles. preferable. When the content ratio is less than 3% by mass, it is difficult not only to reduce the density, but also the effect of increasing the secondary foaming power at the time of molding cannot be obtained, so that the appearance of the foamed molded product is deteriorated. On the other hand, if the content ratio exceeds 10% by mass, shrinkage during foam molding, a delay in adjusting the residual gas in the pre-expanded particles, and a molding cycle become longer, which is not preferable from the viewpoint of productivity.
前記発泡性ポリスチレン系着色樹脂粒子は、物性を損なわない範囲内において、従来から発泡性ポリスチレン系樹脂粒子の製造に使用されている、可塑剤、発泡セル造核剤、充填剤、難燃剤、難燃助剤、滑剤等を必要に応じて適宜使用してもよい。また、ジンクステアレート等の粉末状金属石鹸類を前記発泡性ポリスチレン系着色樹脂粒子の表面に塗布しておけば、発泡性ポリスチレン系着色樹脂粒子の予備発泡工程において予備発泡粒子同士の結合を減少させることができて好ましい。 The expandable polystyrene-based colored resin particles are used in the production of expandable polystyrene-based resin particles, as long as they do not impair the physical properties. Plasticizers, expanded cell nucleating agents, fillers, flame retardants, difficult You may use a fuel adjuvant, a lubricant, etc. suitably as needed. Moreover, if powder metal soaps such as zinc stearate are applied to the surface of the expandable polystyrene colored resin particles, the bonding between the preexpanded particles is reduced in the prefoaming step of the expandable polystyrene colored resin particles. This is preferable.
本発明の発泡性ポリスチレン系着色樹脂粒子は、染料としてアセトアニリド基含有染料を含有するものなので、色むらが無く、一様に着色したポリスチレン系着色樹脂発泡成形体を容易に製造することができる。
また、アセトアニリド基含有染料は、異なる色の染料を複数種組み合わせてポリスチレン系樹脂粒子の表面に含浸させることで、目的の混色を美麗かつ均一に着色できることから、着色のバリエーションを増やすことができる。
Since the expandable polystyrene-based colored resin particles of the present invention contain an acetanilide group-containing dye as a dye, a uniformly colored polystyrene-based colored resin foamed molded article can be easily produced without color unevenness.
In addition, the acetanilide group-containing dye can be colored beautifully and uniformly by impregnating the surface of the polystyrene-based resin particles with a combination of a plurality of dyes of different colors, and therefore, variations in coloring can be increased.
本発明に係る発泡性ポリスチレン系着色樹脂粒子は、ポリスチレン系樹脂粒子を耐圧密閉型の混合機に入れ、撹拌しながら６０℃以上に加熱し、揮発性発泡剤を液状で耐圧密閉型混合機に圧入して揮発性発泡剤をポリスチレン系樹脂粒子に吸収させて発泡性ポリスチレン系樹脂粒子を製造する際に、アセトアニリド基含有染料を界面活性剤と水系媒体に予め分散させた後に添加して発泡性ポリスチレン系着色樹脂粒子を得る方法によって製造される。 The expandable polystyrene colored resin particles according to the present invention are prepared by placing polystyrene resin particles in a pressure-tight sealed mixer and heating to 60 ° C. or higher with stirring to form a volatile foaming agent in a liquid pressure-tight sealed mixer. When a foamable polystyrene resin particle is produced by press-fitting and absorbing a volatile foaming agent into a polystyrene resin particle, the acetanilide group-containing dye is dispersed in advance in a surfactant and an aqueous medium and then added. Manufactured by a method of obtaining polystyrene-based colored resin particles.
本製造方法において、ポリスチレン系樹脂粒子は、分散剤を含んだ水系媒体中に分散させておくことが好ましい。この分散剤としては、例えばピロリン酸マグネシウム、第三リン酸カルシウム等の難水溶性無機化合物やポリビニルアルコール、メチルセルロース、ポリアクリルアミド、ポリビニルピロリドン等の水溶性高分子等が挙げられる。 In this production method, the polystyrene resin particles are preferably dispersed in an aqueous medium containing a dispersant. Examples of the dispersant include poorly water-soluble inorganic compounds such as magnesium pyrophosphate and tricalcium phosphate, and water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyacrylamide, and polyvinyl pyrrolidone.
前記アセトアニリド基含有染料を水系媒体に分散させる際に用いる界面活性剤としては、アニオン系界面活性剤、カチオン系界面活性剤、両イオン系界面活性剤及び非イオン系界面活性剤の中から、使用する染料の分散性等を考慮して適宜選択して用いることができる。 As the surfactant used for dispersing the acetanilide group-containing dye in an aqueous medium, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant are used. The dye can be appropriately selected and used in consideration of the dispersibility of the dye to be used.
本発明の発泡性ポリスチレン系着色樹脂粒子は、発泡樹脂成形体の製造分野において周知の装置及び手法を用い、水蒸気加熱等により加熱して予備発泡し、着色樹脂予備発泡粒子（以下、予備発泡粒子と記す。）とする。この予備発泡粒子は、製造するべき着色樹脂発泡成形体（以下、発泡成形体と記す。）の密度と同等の嵩密度となるように予備発泡される。本発明において、その嵩密度は限定されないが、通常は０．０１０〜０．１０ｇ／ｃｍ３の範囲内とし、０．０１５〜０．０５０ｇ／ｃｍ３の範囲内とするのが好ましい。 The expandable polystyrene-based colored resin particles of the present invention are pre-foamed by heating by steam heating or the like using a well-known apparatus and method in the field of producing foamed resin moldings, and are colored resin pre-foamed particles (hereinafter, pre-foamed particles). .) The pre-expanded particles are pre-expanded so as to have a bulk density equivalent to the density of a colored resin foam-molded product to be manufactured (hereinafter referred to as a foam-molded product). In the present invention, its bulk density is not limited, usually in the range of 0.010~0.10g / cm 3, preferably in the range of 0.015~0.050g / cm 3.
なお、本発明において予備発泡粒子の嵩密度とは、ＪＩＳ Ｋ６９１１：１９９５年「熱硬化性プラスチック一般試験方法」に準拠して測定されたものをいう。
＜予備発泡粒子の嵩密度＞
メスシリンダに予備発泡粒子を５００ｃｍ３の目盛りまで充填する。但し、メスシリンダを水平方向から目視し、予備発泡粒子が一粒でも５００ｃｍ３の目盛りに達していれば、充填を終了する。次に、メスシリンダ内に充填した予備発泡粒子の質量を小数点以下２位の有効数字で秤量し、その質量をＷ（ｇ）とする。次式により予備発泡粒子の嵩密度を算出する。
嵩密度（ｇ／ｃｍ３）＝Ｗ／５００
In the present invention, the bulk density of the pre-expanded particles refers to those measured in accordance with JIS K6911: 1995 “General Test Method for Thermosetting Plastics”.
<Bulk density of pre-expanded particles>
Fill the graduated cylinder with pre-expanded particles to a scale of 500 cm 3 . However, the graduated cylinder is visually observed from the horizontal direction, and if at least one pre-expanded particle reaches the scale of 500 cm 3 , the filling is finished. Next, the mass of the pre-expanded particles filled in the graduated cylinder is weighed with two significant figures after the decimal point, and the mass is defined as W (g). The bulk density of the pre-expanded particles is calculated by the following formula.
Bulk density (g / cm 3 ) = W / 500
＜予備発泡粒子の嵩発泡倍数＞
また、予備発泡粒子の嵩発泡倍数は、次式により算出される数値である。
嵩発泡倍数＝１／嵩密度（ｇ／ｃｍ３）
<Bulk expansion ratio of pre-expanded particles>
Moreover, the bulk expansion ratio of the pre-expanded particles is a numerical value calculated by the following equation.
Bulk foaming factor = 1 / bulk density (g / cm 3 )
前記予備発泡粒子は、発泡樹脂成形体の製造分野において周知の装置及び手法を用い、該予備発泡粒子を成形型のキャビティ内に充填し、水蒸気加熱等により加熱して型内発泡成形し、ポリスチレン系樹脂発泡成形体（以下、発泡成形体と記す）を製造する。
本発明の発泡成形体の密度は特に限定されないが、通常は０．０１０〜０．１０ｇ／ｃｍ３の範囲内とし、０．０１５〜０．０５０ｇ／ｃｍ３の範囲内とするのが好ましい。
The pre-expanded particles are filled in a cavity of a mold using a well-known apparatus and method in the field of manufacturing a foamed resin molded article, heated by steam heating or the like, and subjected to in-mold foam molding. -Based resin foam molded body (hereinafter referred to as foam molded body) is produced.
Although the density of the foamed molded article of the present invention is not particularly limited, usually in the range of 0.010~0.10g / cm 3, preferably in the range of 0.015~0.050g / cm 3.
なお、本発明において発泡成形体の密度とは、ＪＩＳ Ｋ７１２２：１９９９「発泡プラスチック及びゴム−見掛け密度の測定」記載の方法で測定した発泡成形体密度のことである。
＜発泡成形体の密度＞
５０ｃｍ３以上（半硬質および軟質材料の場合は１００ｃｍ３以上）の試験片を材料の元のセル構造を変えない様に切断し、その質量を測定し、次式により算出した。
密度（ｇ／ｃｍ３）＝試験片質量（ｇ）／試験片体積（ｃｍ３）
試験片状態調節、測定用試験片は、成形後７２時間以上経過した試料から切り取り、２３℃±２℃×５０％±５％または２７℃±２℃×６５％±５％の雰囲気条件に１６時間以上放置したものである。
In the present invention, the density of the foamed molded product refers to the density of the foamed molded product measured by the method described in JIS K7122: 1999 “Measurement of foamed plastic and rubber-apparent density”.
<Density of foam molding>
A test piece of 50 cm 3 or more (100 cm 3 or more in the case of semi-rigid and soft materials) was cut so as not to change the original cell structure of the material, its mass was measured, and calculated by the following formula.
Density (g / cm 3 ) = Test piece mass (g) / Test piece volume (cm 3 )
Test piece condition adjustment and measurement test pieces were cut out from samples that had passed 72 hours or more after molding, and were subjected to atmospheric conditions of 23 ° C. ± 2 ° C. × 50% ± 5% or 27 ° C. ± 2 ° C. × 65% ± 5%. It has been left for more than an hour.
＜発泡成形体の発泡倍数＞
また、発泡成形体の発泡倍数は次式により算出される数値である。
発泡倍数＝１／密度（ｇ／ｃｍ３）
<Folding multiple of foamed molded product>
Further, the expansion factor of the foamed molded product is a numerical value calculated by the following equation.
Foaming factor = 1 / density (g / cm 3 )
本発明の発泡成形体は、前記発泡性ポリスチレン系着色樹脂粒子を加熱して予備発泡し、得られた予備発泡粒子を成形型のキャビティ内に充填し加熱し型内発泡成形して得られたものなので、色むらが無く、一様に着色した美麗な外観の発泡成形体を提供できる。 The foamed molded product of the present invention was obtained by heating and pre-expanding the expandable polystyrene-based colored resin particles, filling the obtained pre-expanded particles in a cavity of a mold, and heating and in-mold foam molding. Therefore, it is possible to provide a foamed molded article having a beautiful appearance that is uniformly colored and has no color unevenness.
本発明の発泡成形体の用途は、特に限定されないが、色むらが無く、一様に着色した美麗な外観の製品が得られることから、例えば、建材用断熱材、食品容器（魚箱、野菜収容箱など）、搬送容器、保冷断熱容器、装飾ブロック、土木用ブロックなどの用途において好適に使用し得る。 The use of the foamed molded article of the present invention is not particularly limited, but it is possible to obtain a uniform appearance and a beautifully colored product having no color unevenness. For example, heat insulating materials for building materials, food containers (fish boxes, vegetables Storage boxes, etc.), transport containers, cold insulation containers, decorative blocks, civil engineering blocks, and the like.
以下、実施例によって本発明をより具体的に説明するが、以下の実施例は本発明の例示に過ぎず、本発明は以下の実施例の記載に限定されるものではない。
以下の各実施例、比較例において、「質量部」は「部」と略記し、「質量％」は「％」と略記している。
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, a following example is only the illustration of this invention and this invention is not limited to description of a following example.
In the following Examples and Comparative Examples, “parts by mass” is abbreviated as “parts”, and “mass%” is abbreviated as “%”.
［実施例１］
内容積６リットルのオートクレーブに、水性媒体として純水２２００部、ピロ燐酸マグネシウム５．０部、ドデシルベンゼンスルホン酸ソーダ１．２部の混合物を入れ、ポリスチレン系樹脂粒子（Ｍｗ：３０万）２１００部を加え、回転数２５０ｒｐｍで撹拌し、水性媒体中に懸濁したものを３０℃に保持した。
次に、青色染料（ＤｉｓｐｅｒｓｅＢｌｕｅ１６５）２．７部を予めドデシルベンゼンスルホン酸ソーダ０．２部、純水１００部に予備分散させたものをオートクレーブ内に投入した。
その後、この中にシクロヘキサン４５部、発泡剤としてブタン１６０部を圧入した。
続いて１００℃に昇温してこの温度に３時間保持して含浸を完結させ、その後冷却して発泡性ポリスチレン系着色樹脂粒子を得た。
こうして得られた発泡性粒子を嵩発泡倍数５０倍に予備発泡させたところ、色むらが０．０５％程度で殆ど認められない青色の予備発泡粒子を得た。
この予備発泡粒子を２４時間室温に放置したのち、４００×３００×１００ｍｍの大きさのキャビティを有する成形型に入れ、ゲージ圧０．７ｋｇ／ｃｍ２の水蒸気を３０秒間成形型内に導入して発泡させ、その後５分間冷却して発泡成形体を得た。
この発泡成形体を５０℃の乾燥室に入れて１日乾燥し、外観を目視で調べた。その結果、得られた発泡成形体は、発泡粒子同士が互いによく融着し、青色で色むらの少ない良質のものであった。
ここで、色むらは、目視で確認し、発泡成形体全体にわたり均一な着色状態であるものを、色むら無し、○（良好）とし、発泡成形体のいずれかに色むら（色の濃淡、色抜け等）があるものを、色むら有り、×（不良）として評価した。その結果を表１に記す。
[Example 1]
A mixture of 2200 parts pure water, 5.0 parts magnesium pyrophosphate and 1.2 parts sodium dodecylbenzenesulfonate as an aqueous medium is placed in an autoclave having an internal volume of 6 liters, and 2100 parts of polystyrene resin particles (Mw: 300,000). The mixture was stirred at a rotational speed of 250 rpm, and the suspension in an aqueous medium was kept at 30 ° C.
Next, 2.7 parts of a blue dye (Disperse Blue 165) preliminarily dispersed in 0.2 part of sodium dodecylbenzenesulfonate and 100 parts of pure water was charged into the autoclave.
Thereafter, 45 parts of cyclohexane and 160 parts of butane as a blowing agent were press-fitted therein.
Subsequently, the temperature was raised to 100 ° C. and maintained at this temperature for 3 hours to complete the impregnation, and then cooled to obtain expandable polystyrene-based colored resin particles.
When the expandable particles thus obtained were pre-expanded to a bulk expansion ratio of 50 times, blue pre-expanded particles with color irregularities of about 0.05% and hardly recognized were obtained.
After leaving the pre-expanded particles at room temperature for 24 hours, the pre-expanded particles are put into a mold having a cavity of 400 × 300 × 100 mm, and water vapor with a gauge pressure of 0.7 kg / cm 2 is introduced into the mold for 30 seconds. It was made to foam, and it cooled after that for 5 minutes, and obtained the foaming molding.
The foamed molded product was placed in a drying room at 50 ° C. and dried for one day, and the appearance was examined visually. As a result, the obtained foamed molded article was of a good quality, in which the foamed particles were well fused with each other and were blue with little color unevenness.
Here, the color unevenness is visually confirmed, and in a uniformly colored state throughout the foam molded article, no color unevenness, ○ (good), color unevenness (color shading, Those with color loss etc. were evaluated as having color unevenness and x (defect). The results are shown in Table 1.
［実施例２］
青色染料に代えて、赤色染料（ＤｉｓｐｅｒｓｅＲｅｄ８２）２．７部を使用したこと以外は、実施例１と同様にして、発泡成形体を製造した。
この発泡成形体を５０℃の乾燥室に入れて１日乾燥し、外観を目視で調べた。その結果、得られた発泡成形体は、発泡粒子同士が互いによく融着し、赤色で色むらの少ない良質のものであった。色むらの評価結果を表１に記す。
[Example 2]
A foamed molded article was produced in the same manner as in Example 1 except that 2.7 parts of a red dye (Disperse Red 82) was used instead of the blue dye.
The foamed molded product was placed in a drying room at 50 ° C. and dried for one day, and the appearance was examined visually. As a result, the obtained foamed molded article was of a good quality, in which the foamed particles were well fused with each other and were red with little color unevenness. The evaluation results of color unevenness are shown in Table 1.
［実施例３］
青色染料に代えて、黄色染料（ＤｉｓｐｅｒｓｅＹｅｌｌｏｗ３）２．７部を使用したこと以外は、実施例１と同様にして、発泡成形体を製造した。
この発泡成形体を５０℃の乾燥室に入れて１日乾燥し、外観を目視で調べた。その結果、得られた発泡成形体は、発泡粒子同士が互いによく融着し、黄色で色むらの少ない良質のものであった。色むらの評価結果を表１に記す。
[Example 3]
A foamed molded article was produced in the same manner as in Example 1 except that 2.7 parts of a yellow dye (Disperse Yellow 3) was used instead of the blue dye.
The foamed molded product was placed in a drying room at 50 ° C. and dried for one day, and the appearance was examined visually. As a result, the obtained foamed molded product was a good quality product in which the foamed particles were well fused with each other and were yellow with little uneven color. The evaluation results of color unevenness are shown in Table 1.
［実施例４］
使用する染料を青色染料（ＤｉｓｐｅｒｓｅＢｌｕｅ１６５）３．０部、赤色染料（ＤｉｓｐｅｒｓｅＲｅｄ８２）２．５部を併用したこと以外は、実施例１と同様にして、発泡成形体を製造した。
この発泡成形体を５０℃の乾燥室に入れて１日乾燥し、外観を目視で調べた。その結果、得られた発泡成形体は、発泡粒子同士が互いによく融着し、グレー色で色むらの少ない良質のものであった。色むらの評価結果を表１に記す。
[Example 4]
A foamed molded article was produced in the same manner as in Example 1 except that 3.0 parts of a blue dye (DisperseBlue165) and 2.5 parts of a red dye (DisperseRed82) were used in combination.
The foamed molded product was placed in a drying room at 50 ° C. and dried for one day, and the appearance was examined visually. As a result, the obtained foamed molded article was a good quality product in which the foamed particles were well fused with each other, were gray and had little color unevenness. The evaluation results of color unevenness are shown in Table 1.
［比較例１］
染料としてアセトアニリド基を持たない青色染料（ＳｏｌｖｅｎｔＢｌｕｅ７８）を使用したこと以外は、実施例１と同様にして発泡成形体を得た。
この発泡成形体を５０℃の乾燥室に入れて１日乾燥し、外観を目視で調べた。その結果、得られた発泡成形体は、色むらが多く、外観に劣るものであった。色むらの評価結果を表１に記す。
[Comparative Example 1]
A foam molded article was obtained in the same manner as in Example 1 except that a blue dye having no acetanilide group (Solvent Blue 78) was used as the dye.
The foamed molded product was placed in a drying room at 50 ° C. and dried for one day, and the appearance was examined visually. As a result, the obtained foamed molded article had many color irregularities and was inferior in appearance. The evaluation results of color unevenness are shown in Table 1.
［比較例２］
染料としてアセトアニリド基を持たない青色染料（ＤｉｓｐｅｒｓｅＢｌｕｅ１０２）を使用したこと以外は、実施例１と同様にして発泡成形体を得た。
この発泡成形体を５０℃の乾燥室に入れて１日乾燥し、外観を目視で調べた。その結果、得られた発泡成形体は、色むらが多く、外観に劣るものであった。色むらの評価結果を表１に記す。
[Comparative Example 2]
A foam molded article was obtained in the same manner as in Example 1 except that a blue dye having no acetanilide group (Disperse Blue 102) was used as the dye.
The foamed molded product was placed in a drying room at 50 ° C. and dried for one day, and the appearance was examined visually. As a result, the obtained foamed molded article had many color irregularities and was inferior in appearance. The evaluation results of color unevenness are shown in Table 1.
表１の結果から、アセトアニリド基含有色素を用いて染色した実施例１〜４は、美麗に着色されて色むらの少ない良質の発泡成形体が得られた。
一方、アセトアニリド基を持たない染料を用いた比較例１，２で得られた発泡成形体は、色むらが多く、外観に劣るものであった。
From the results of Table 1, Examples 1 to 4 dyed with an acetanilide group-containing dye were beautifully colored, and high-quality foam molded articles with little color unevenness were obtained.
On the other hand, the foamed molded products obtained in Comparative Examples 1 and 2 using a dye having no acetanilide group had many color unevenness and poor appearance.
本発明は、発泡剤を含み、着色されたポリスチレン系樹脂粒子からなる発泡性ポリスチレン系着色樹脂粒子とその製造方法に関し、特に、色むらが無く、一様に着色した発泡成形体を容易に製造することができる発泡性ポリスチレン系着色樹脂粒子とその製造方法を提供する。また本発明は、前記発泡性ポリスチレン系着色樹脂粒子を予備発泡させて得られた予備発泡粒子、該予備発泡粒子を型内発泡成形して得られた発泡成形体、建材用断熱材、食品容器、搬送容器、保冷断熱容器、装飾ブロック及び土木用ブロックを提供する。 The present invention relates to an expandable polystyrene-based colored resin particle comprising a foaming agent and consisting of colored polystyrene-based resin particles and a method for producing the same, and in particular, easily producing a foamed molded product that is uniformly colored and has no color unevenness. An expandable polystyrene colored resin particle that can be produced and a method for producing the same. The present invention also provides pre-foamed particles obtained by pre-foaming the expandable polystyrene-based colored resin particles, foam-molded articles obtained by in-mold foam-molding the pre-foamed particles, heat insulating materials for building materials, food containers The present invention provides a transport container, a cold insulation heat insulation container, a decorative block, and a civil engineering block.
Claims (16)
アセトアニリド基含有染料を界面活性剤と水系媒体に予め分散させた後に添加して発泡性ポリスチレン系着色樹脂粒子を得ることを特徴とする発泡性ポリスチレン系着色樹脂粒子の製造方法。 The polystyrene resin particles are put into a pressure-resistant sealed mixer, heated to 60 ° C. or higher with stirring, and the volatile foaming agent is pressed into the pressure-resistant sealed mixer in a liquid state to convert the volatile foaming agent into the polystyrene resin particles. In the method for producing expandable polystyrene resin particles by absorbing,
A method for producing expandable polystyrene-based colored resin particles, wherein an acetanilide group-containing dye is dispersed in a surfactant and an aqueous medium before being added to obtain expandable polystyrene-based colored resin particles.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014177540A (en) * | 2013-03-14 | 2014-09-25 | Sekisui Plastics Co Ltd | Foaming polystyrene-based coloring composite resin particle, foam particle, foam molding and production methods for the colored composite resin particle, foam particle and foam molding |
| JP2021042346A (en) * | 2019-09-13 | 2021-03-18 | 株式会社ジェイエスピー | Foamable colored resin particle, method for producing the same and foam particle molding |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014177540A (en) * | 2013-03-14 | 2014-09-25 | Sekisui Plastics Co Ltd | Foaming polystyrene-based coloring composite resin particle, foam particle, foam molding and production methods for the colored composite resin particle, foam particle and foam molding |
| JP2021042346A (en) * | 2019-09-13 | 2021-03-18 | 株式会社ジェイエスピー | Foamable colored resin particle, method for producing the same and foam particle molding |
| JP7273309B2 (en) | 2019-09-13 | 2023-05-15 | 株式会社ジェイエスピー | Expandable colored resin particles, method for producing the same, and expanded particle molded product |
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