JP5635392B2 - Method for producing expandable polystyrene-based colored resin particles, method for producing colored resin pre-foamed particles, and method for producing colored resin foam molded article - Google Patents
Method for producing expandable polystyrene-based colored resin particles, method for producing colored resin pre-foamed particles, and method for producing colored resin foam molded article Download PDFInfo
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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、着色むらが無く、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に関する。 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. 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 molded article.
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。
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成形体を製造するには、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。
しかし、カーボンブラックを含んだ発泡性ポリスチレン系着色樹脂粒子を製造するには、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樹脂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。
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.
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 a foam-molded article colored in gray, carbon black has generally been used as a colorant.
However, in order to produce expandable polystyrene colored resin particles containing carbon black, it is necessary to add at the polymerization stage of the polystyrene resin, and when impregnating the foaming agent, the resin particles can absorb carbon black. The manufacturing process becomes complicated.
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.
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、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。
また、上述した従来方法において染料又は顔料の離脱を防止するためには、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。
In the conventional method, the coloring of the expandable polystyrene resin particles tends to be uneven. In particular, when two or more kinds of dyes are mixed and used, uneven coloring easily occurs, and a foamed molded product produced using expandable polystyrene-based colored resin particles tends to be inferior in appearance.
Further, in order to prevent the dye or pigment from detaching in the conventional method described above, there is a method of coating the surface of the resin particle with the dye or pigment using a coating agent. In this method, the inside can be uniformly colored. In addition to being unable to do so, there is a drawback that the manufacturing process becomes complicated due to the extra coating process.
本発明は、前記事情に鑑みてなされ、着色むらが無く、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の提供を課題とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an expandable polystyrene-based colored resin particle that can easily produce a foamed molded product that is uniformly colored and that is uniformly colored, and a method for producing the same.
本発明者は、発泡成形体を青色に着色する場合や、２種以上の染料を併用してグレー等に着色する場合に、染料としてＳｏｌｖｅｎｔＢｌｕｅ７８をした場合に、着色むらが生じ難く、均一に着色できることを見出し、本発明を完成させた。
本発明は、前記課題を解決するために、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、染料としてＳｏｌｖｅｎｔＢｌｕｅ７８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 inventor, when coloring a foamed molded product in blue, or when using two or more dyes in combination with gray or the like, when SolventBlue 78 is used as a dye, uneven coloring is unlikely to occur and the color is uniformly colored. The present invention has been completed by finding out what can be done.
In order to solve the above-mentioned problems, the present invention provides expandable polystyrene colored resin particles characterized in that the expandable polystyrene colored resin particles colored with a dye contain Solvent Blue 78 as 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、ＳｏｌｖｅｎｔＢｌｕｅ７８を０．００３〜０．４質量％の範囲で含有することが好ましい。 In the expandable polystyrene-based colored resin particles of the present invention, Solvent Blue 78 is preferably contained in the range of 0.003 to 0.4 mass%.
本発明の発泡性ポリスチレン系着色樹脂粒子において、ＳｏｌｖｅｎｔＢｌｕｅ７８と併用して、青色以外のアントラキノン系染料、アゾ系染料、キノリン系染料から成る群から選択される１種又は２種以上の染料を含有させてもよい。 In the expandable polystyrene colored resin particles of the present invention, in combination with Solvent Blue 78, one or more dyes selected from the group consisting of anthraquinone dyes other than blue, azo dyes, and quinoline dyes are contained. May be.
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、ポリオレフィン系樹脂が含有されている構成としてもよい。 In the expandable polystyrene-based colored resin particles of the present invention, the expandable polystyrene-based colored resin particles may include a polyolefin-based resin.
また本発明は、ポリスチレン系樹脂粒子を耐圧容器内に入れ、さらに染料と発泡剤を投入してポリスチレン系樹脂粒子に発泡剤と染料とを含浸させて発泡性ポリスチレン系着色樹脂粒子を製造する方法において、前記染料がＳｏｌｖｅｎｔＢｌｕｅ７８を含有し、該染料を水性媒体に予め分散させて投入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の製造方法を提供する。 Further, the present invention provides a method for producing expandable polystyrene-based colored resin particles by placing polystyrene-based resin particles in a pressure-resistant container, and further adding a dye and a foaming agent to impregnate the polystyrene-based resin particles with the foaming agent and the dye. The method of producing expandable polystyrene-based colored resin particles is characterized in that the dye contains Solvent Blue 78, and the dye is dispersed in an aqueous medium in advance.
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、ポリスチレン系樹脂粒子を水系媒体とともに耐圧容器内に入れ、前記染料を投入してポリスチレン系樹脂粒子に染料を吸収させた後、該容器内を６０℃以上に昇温し、該容器内に発泡剤を圧入してポリスチレン系樹脂粒子に発泡剤を吸収させることが好ましい。 In the method for producing expandable polystyrene-based colored resin particles of the present invention, the polystyrene-based resin particles are placed in a pressure-resistant container together with an aqueous medium, the dye is added, and the polystyrene-based resin particles absorb the dye. It is preferable that the temperature is raised to 60 ° C. or higher, and a foaming agent is press-fitted into the container so that the polystyrene-based resin particles absorb the foaming agent.
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、発泡性ポリスチレン系着色樹脂粒子中のＳｏｌｖｅｎｔＢｌｕｅ７８含有量が０．００３〜０．４質量％の範囲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 content of Solvent Blue 78 in the expandable polystyrene colored resin particles is preferably in the range of 0.003 to 0.4 mass%.
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ＳｏｌｖｅｎｔＢｌｕｅ７８と併用して、青色以外のアントラキノン系染料、アゾ系染料、キノリン系染料から成る群から選択される１種又は２種以上の染料を含有させてもよい。 In the method for producing expandable polystyrene-based colored resin particles of the present invention, in combination with the Solvent Blue 78, one or more selected from the group consisting of anthraquinone dyes other than blue, azo dyes, and quinoline dyes A dye may be included.
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、発泡性ポリスチレン系着色樹脂粒子中に、ポリオレフィ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-based colored resin particles of the present invention, the expandable polystyrene-based colored resin particles may include a polyolefin-based 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成形型のキャビティ内に充填し加熱して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 filling the colored resin pre-foamed particles in a cavity of a molding die and heating to form in-mold foam molding.
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、染料としてＳｏｌｖｅｎｔＢｌｕｅ７８を含有するものなので、着色むらが無く、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。
また、ＳｏｌｖｅｎｔＢｌｕｅ７８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 colored resin particles of the present invention contain Solvent Blue 78 as a dye in the expandable polystyrene colored resin particles colored with a dye, there is no uneven coloring, and a uniformly colored expanded molded article can be easily obtained. Can be manufactured.
In addition, Solvent Blue 78 can be colored beautifully and uniformly by combining a plurality of types of dyes of different colors and impregnating the surface of the polystyrene resin particles, so that 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の製造方法は、前述した通り美麗に着色された発泡成形体が得られる発泡性ポリスチレン系着色樹脂粒子を容易且つ低コストで製造することができる。 As described above, the method for producing expandable polystyrene-based colored resin particles of the present invention can easily and inexpensively produce expandable polystyrene-based colored resin particles from which a beautifully colored expanded molded article can be obtained.
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、染料としてＳｏｌｖｅｎｔＢｌｕｅ７８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 Solvent Blue 78 as a 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系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おいて、前記ＳｏｌｖｅｎｔＢｌｕｅ７８の含有量は、０．００３〜０．４質量％の範囲内であることが好ましく、０．００５〜０．３０質量％の範囲内であることがより好ましい。ＳｏｌｖｅｎｔＢｌｕｅ７８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、ＳｏｌｖｅｎｔＢｌｕｅ７８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、成形性が低下する為に好ましくない。 In the expandable polystyrene-based colored resin particles of the present invention, the content of the Solvent Blue 78 is preferably in the range of 0.003 to 0.4% by mass, and in the range of 0.005 to 0.30% by mass. More preferably. If the content of SolventBlue 78 is less than the above range, the degree of coloration of the foamed molded product finally obtained will be weak. On the other hand, if the content of Solvent Blue 78 exceeds the above range, it is not preferable because not only the cost is increased but also the moldability is lowered.
本発明の発泡性ポリスチレン系着色樹脂粒子において、ＳｏｌｖｅｎｔＢｌｕｅ７８と色の異なる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 mixed color by containing Solvent Blue 78 and another type of dye having a different color. The kind and combination of the dyes for obtaining the color mixture are not particularly limited.
ＳｏｌｖｅｎｔＢｌｕｅ７８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（ＣＯＬＯＲ ＩＮＤＥＸ ＧＥＮＥＲＩＣ ＮＡＭＥ、以下、同じ）、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１１４、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１６３、ＳｏｌｖｅｎｔＹｅｌｌｏｗ９３、ＳｏｌｖｅｎｔＹｅｌｌｏｗ３３、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１６、ＳｏｌｖｅｎｔＧｒｅｅｎ５、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１０４、ＳｏｌｖｅｎｔＯｒａｎｇｅ６０、ＳｏｌｖｅｎｔＹｅｌｌｏｗ１４、ＳｏｌｖｅｎｔＯｒａｎｇｅ６３、ＶａｔＲｅｄ４１、ＳｏｌｖｅｎｔＲｅｄ１４９、ＳｏｌｖｅｎｔＲｅｄ１１１、ＳｏｌｖｅｎｔＲｅｄ１３５、ＳｏｌｖｅｎｔＲｅｄ１７９、ＳｏｌｖｅｎｔＲｅｄ１４６、ＳｏｌｖｅｎｔＲｅｄ２２、ＳｏｌｖｅｎｔＲｅｄ５２、ＳｏｌｖｅｎｔＶｉｏｌｅｔ３１、ＳｏｌｖｅｎｔＶｉｏｌｅｔ１３、ＤｉｓｐｅｒｓｅＢｌｕｅ１６５、ＤｉｓｐｅｒｓｅＢｌｕｅ１５、ＳｏｌｖｅｎｔＧｒｅｅｎ３、ＰｉｇｍｅｎｔＲｅｄ１７０等が挙げられる。 SolventBlue78 when combining other dyes, other dyes, for example, SolventYellow167 (COLOR INDEX GENERIC NAME, hereinafter the same), SolventYellow114, SolventYellow163, SolventYellow93, SolventYellow33, SolventYellow16, SolventGreen5, SolventYellow104, SolventOrange60, SolventYellow14, SolventOrange63, VatRed41 , SolventRed149, SolventRed111, SolventRed135, SolventRed179, SolventRed146, Solv ntRed22, SolventRed52, SolventViolet31, SolventViolet13, DisperseBlue165, DisperseBlue15, 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.
前記発泡剤の含有量は、ポリスチレン系樹脂粒子に対して２〜１０質量％の範囲が好ましく、３〜９質量％がより好ましい。前記含有量が２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、含有量が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 2 to 10% by mass, more preferably 3 to 9% by mass with respect to the polystyrene resin particles. When the content is less than 2% by mass, not only is it difficult to reduce the density, but 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 becomes inferior. On the other hand, if the content exceeds 10% by mass, the shrinkage during foam molding, the adjustment time of the residual gas in the pre-expanded particles is delayed, and the molding cycle becomes long, 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ＳｏｌｖｅｎｔＢｌｕｅ７８を含有するものなので、着色むらが無く、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。
また、ＳｏｌｖｅｎｔＢｌｕｅ７８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 colored resin particles of the present invention contain Solvent Blue 78 as a dye, there is no uneven coloring, and a uniformly colored expanded molded article can be easily produced.
In addition, Solvent Blue 78 can be colored beautifully and uniformly by combining a plurality of types of dyes of different colors and impregnating the surface of the polystyrene resin particles, so that 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容器内に入れ、さらに染料と発泡剤を投入してポリスチレン系樹脂粒子に発泡剤と染料とを含浸させて発泡性ポリスチレン系着色樹脂粒子を製造する際に、ＳｏｌｖｅｎｔＢｌｕｅ７８を含有する染料を水性媒体に予め分散させて投入し、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-based colored resin particles according to the present invention are obtained by placing polystyrene-based resin particles in a pressure-resistant container, and further adding a dye and a foaming agent so that the polystyrene-based resin particles are impregnated with the foaming agent and the dye. When the colored resin particles are produced, a dye containing Solvent Blue 78 is dispersed in an aqueous medium in advance and added to obtain expandable colored polystyrene 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。
前記分散剤としては、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ＳｏｌｖｅｎｔＢｌｕｅ７８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 when dispersing the Solvent Blue 78 in an aqueous medium, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant may be used. It can be appropriately selected and used in consideration of dispersibility and the like.
本製造方法は、ポリスチレン系樹脂粒子を水系媒体とともに耐圧容器内に入れ、前記染料を投入してポリスチレン系樹脂粒子に染料を吸収させた後、該容器内を６０℃以上に昇温し、該容器内に発泡剤を圧入してポリスチレン系樹脂粒子に発泡剤を吸収させて発泡性ポリスチレン系着色樹脂粒子を製造することが好ましい。 In this production method, polystyrene resin particles are placed in a pressure-resistant container together with an aqueous medium, the dye is added and the polystyrene resin particles absorb the dye, and then the temperature in the container is raised to 60 ° C. or higher. It is preferable to produce foamable polystyrene-based colored resin particles by press-fitting a foaming agent into the container and allowing the polystyrene-based resin particles to absorb the foaming agent.
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は、前述した通り美麗に着色された発泡成形体が得られる発泡性ポリスチレン系着色樹脂粒子を容易且つ低コストで製造することができる。 As described above, the method for producing expandable polystyrene-based colored resin particles of the present invention can easily and inexpensively produce expandable polystyrene-based colored resin particles from which a beautifully colored expanded molded article can be obtained.
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 referred to as 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 was 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、着色むらが無く、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 with uniform coloring and no uneven coloring.
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、水系媒体として純水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、可塑剤としてシクロヘキサン４５部を入れ、ホモミキサーで撹拌して懸濁液を調製し、該液中にポリスチレン系樹脂粒子（Ｍｗ：３０万）２１００部を加え、撹拌羽根（回転数２５０ｒｐｍ）で撹拌し、水系媒体中に懸濁したものを３０℃に保持した。
次に、２．５部のＳｏｌｖｅｎｔＢｌｕｅ７８を予めドデシルベンゼンスルホン酸ソーダ０．２ｇを含む純水１００ｇの水系媒体中に予備分散させたものを、前記オートクレーブ内に投入した。
その後、発泡剤としてブタン２００部を圧入した。続いてオートクレーブ内を９０℃に昇温し、この温度に５時間保持した。その後、２５℃まで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ポリスチレン系着色樹脂粒子５ｋｇを、松坂貿易社製のレーディゲミキサーＭ２０型（内容積２０リットル）に投入した。次いでステアリン酸亜鉛２．５ｇ、１２−ヒドロキシステアリン酸トリグリセライド２．５ｇ、ステアリン酸モノグリセライド２．５ｇを順次投入し２３０ｒｐｍで３分間撹拌した。次いで重量平均分子量３００であるポリエチレングリコール２．５ｇを投入し２３０ｒｐｍで５分間撹拌し、樹脂粒子表面を被覆した。
この被覆後の発泡性ポリスチレン系着色樹脂粒子を内容量約４０リットルの小型バッチ式予備発泡機に入れ、常圧下でゲージ圧力０．０５ＭＰａの水蒸気で加熱し、嵩発泡倍数６０倍に予備発泡し、予備発泡粒子を得た。
得られた予備発泡粒子を２０℃で２４時間放置し、乾燥、熟成させた後、面圧計が取り付けられ、外寸３００×４００×２５ｍｍの板型の成形品製造用のキャビティを有する金型を成形機に取付け、該キャビティ内に前記予備発泡粒子を充填し、水蒸気加熱による型内発泡成形を行った。成形機は積水工機製作所社製のＡＣＥ−３ＳＰを用い、ＱＳ成形モードでゲージ圧０．７ｋｇ／ｃｍ２、金型加熱３秒、一方加熱８秒、逆一方加熱１秒、両面加熱１０秒、水冷５秒、設定取出面圧０．０２ＭＰａの条件で型内発泡成形を行って発泡成形体を製造した。
得られた発泡成形体を４０℃の乾燥室に入れて１日乾燥し、外観を目視で調べ、以下の＜着色むらの測定評価＞に基づいて評価した。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合い、美麗な青色で着色むらの少ない良質なものであった。結果を表１に記す。
[Example 1]
In an autoclave having an internal volume of 6 liters, 2200 parts of pure water as an aqueous medium, 5.0 parts of magnesium pyrophosphate, 1.2 parts of sodium dodecylbenzenesulfonate and 45 parts of cyclohexane as a plasticizer are stirred and suspended by a homomixer. A turbid liquid was prepared, 2100 parts of polystyrene resin particles (Mw: 300,000) were added to the liquid, stirred with a stirring blade (rotation speed: 250 rpm), and suspended in an aqueous medium at 30 ° C. .
Next, 2.5 parts of Solvent Blue 78 preliminarily dispersed in an aqueous medium of 100 g of pure water containing 0.2 g of sodium dodecylbenzenesulfonate was charged into the autoclave.
Thereafter, 200 parts of butane was press-fitted as a foaming agent. Subsequently, the inside of the autoclave was heated to 90 ° C. and kept at this temperature for 5 hours. Then, it cooled to 25 degreeC and the expandable polystyrene-type colored resin particle was obtained.
5 kg of the expandable polystyrene-based colored resin particles obtained in this manner were put into a Ladige mixer M20 type (internal volume 20 liters) manufactured by Matsuzaka Trading Co., Ltd. Next, 2.5 g of zinc stearate, 2.5 g of 12-hydroxystearic acid triglyceride, and 2.5 g of stearic acid monoglyceride were sequentially added and stirred at 230 rpm for 3 minutes. Next, 2.5 g of polyethylene glycol having a weight average molecular weight of 300 was added and stirred at 230 rpm for 5 minutes to coat the resin particle surfaces.
The expanded polystyrene colored resin particles after coating are put into a small batch type pre-foaming machine with an internal volume of about 40 liters, heated under normal pressure with water vapor with a gauge pressure of 0.05 MPa, and pre-foamed to a bulk foaming factor of 60 times. Pre-expanded particles were obtained.
The obtained pre-expanded particles were left at 20 ° C. for 24 hours, dried and aged, and then a die having a cavity for manufacturing a plate-shaped molded article having an outer dimension of 300 × 400 × 25 mm was attached. It was attached to a molding machine, the pre-expanded particles were filled into the cavity, and in-mold foam molding was performed by steam heating. ACE-3SP manufactured by Sekisui Koki Seisakusho Co., Ltd. is used as the molding machine. In the QS molding mode, gauge pressure 0.7 kg / cm 2 , mold heating 3 seconds, one heating 8 seconds, reverse one heating 1 second, double-side heating 10 seconds. In-mold foam molding was carried out under conditions of water cooling for 5 seconds and a set take-out surface pressure of 0.02 MPa to produce a foam molded article.
The obtained foamed molded article was put in a drying room at 40 ° C. and dried for one day. The appearance was visually examined and evaluated based on the following <Measurement evaluation of uneven coloring>. The obtained foamed molded article was of a good quality with foamed particles that fused well with each other, beautiful blue, and less uneven coloring. The results are shown in Table 1.
＜着色むらの測定評価＞
発泡成形体を目視で確認し、板型成形品の主面（４００×３００ｍｍ）内で着色むらが発生している発泡粒の数を調べた。
前記主面内で着色むらが発生している発泡粒が３粒以下であり、かつ全体にわたり均一な着色状態であるものを、着色むら無し（良好（○））とし、前記主面内に着色むらが発生している発泡粒が３粒以上あり、さらに色の濃淡、色抜け等があるものを、着色むら有り（不良（×））として評価した。
<Measurement evaluation of uneven coloring>
The foamed molded product was visually confirmed, and the number of foamed particles in which coloring unevenness occurred within the main surface (400 × 300 mm) of the plate mold product was examined.
When the number of foamed particles in which uneven coloring occurs in the main surface is 3 or less and the color is uniform throughout, the coloring is not uneven (good (◯)) and the main surface is colored. When there were 3 or more foamed particles with unevenness, and those with color shading, color loss, etc., they were evaluated as having uneven coloring (defect (x)).
［実施例２］
ＳｏｌｖｅｎｔＢｌｕｅ７８の量を０．１部としたこと以外は、実施例１と同様にして発泡成形体を製造した。
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、青色で着色むらの少ない美麗な外観であった。着色むらの評価結果を表１に記す。
[Example 2]
A foam molded article was produced in the same manner as in Example 1 except that the amount of Solvent Blue 78 was 0.1 part.
The obtained foamed molded article had a beautiful appearance in which the foamed particles were well fused with each other and were blue with little uneven coloring. The evaluation results of uneven coloring are shown in Table 1.
［実施例３］
ＳｏｌｖｅｎｔＢｌｕｅ７８の量を８．５部としたこと以外は、実施例１と同様にして発泡成形体を製造した。
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、青色で着色むらの少ない美麗な外観であった。着色むらの評価結果を表１に記す。
[Example 3]
A foam molded article was produced in the same manner as in Example 1 except that the amount of Solvent Blue 78 was 8.5 parts.
The obtained foamed molded article had a beautiful appearance in which the foamed particles were well fused with each other and were blue with little uneven coloring. The evaluation results of uneven coloring are shown in Table 1.
［実施例４］
２．７部のＳｏｌｖｅｎｔＢｌｕｅ７８と２．５部のＤｉｓｐｅｒｓｅＲｅｄ９と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。
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、グレー色で着色むらの少ない美麗な外観であった。着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 2.7 parts of Solvent Blue 78 and 2.5 parts of Disperse Red 9 were used in combination.
The obtained foamed molded article had a beautiful appearance in which the foamed particles were well fused with each other, were gray, and had little uneven coloring. The evaluation results of uneven coloring are shown in Table 1.
［比較例１］
染料としてＳｏｌｖｅｎｔＢｌｕｅ７８ではないアントラキノン系染料のＳｏｌｖｅｎｔＢｌｕｅ８７を同量用い、それ以外は実施例１と同様にして発泡成形体を製造した。
得られた発泡成形体は、青色であるが着色むらが多く、外観が劣るものであった。着色むらの評価結果を表１に記す。
[Comparative Example 1]
A foam-molded article was produced in the same manner as in Example 1 except that the same amount of an anthraquinone dye Solvent Blue 87 other than Solvent Blue 78 was used.
The obtained foamed molded product was blue but had many uneven coloring and poor appearance. The evaluation results of uneven coloring are shown in Table 1.
［比較例２］
染料としてＳｏｌｖｅｎｔＢｌｕｅ７８ではないアントラキノン系染料のＳｏｌｖｅｎｔＢｌｕｅ５８を同量用い、それ以外は実施例１と同様にして発泡成形体を製造した。
得られた発泡成形体は、青色であるが着色むらが多く、外観が劣るものであった。着色むらの評価結果を表１に記す。
[Comparative Example 2]
A foam molded article was produced in the same manner as in Example 1 except that the same amount of the anthraquinone dye SolventBlue 58 other than SolventBlue 78 was used as the dye.
The obtained foamed molded product was blue but had many uneven coloring and poor appearance. The evaluation results of uneven coloring are shown in Table 1.
［比較例３］
染料としてＳｏｌｖｅｎｔＢｌｕｅ７８ではないアントラキノン系染料のＳｏｌｖｅｎｔＢｌｕｅ６３を２．７部と、ＤｉｓｐｅｒｓｅＲｅｄ９を２．５部とを併用し、それ以外は実施例１と同様にして発泡成形体を製造した。
得られた発泡成形体は、グレー色であるが着色むらが多く、外観が劣るものであった。着色むらの評価結果を表１に記す。
[Comparative Example 3]
A foam molded article was produced in the same manner as in Example 1 except that 2.7 parts of SolventBlue 63, which is an anthraquinone dye other than SolventBlue 78, and 2.5 parts of DisperseRed9 were used in combination.
The obtained foamed molded product was gray, but had many uneven coloring and poor appearance. The evaluation results of uneven coloring are shown in Table 1.
表１の結果から、染料としてＳｏｌｖｅｎｔＢｌｕｅ７８を用いた実施例１〜４は、美麗に着色され、着色むらの少ない良質な発泡成形体が得られた。
一方、ＳｏｌｖｅｎｔＢｌｕｅ７８とは異なる染料を用いた比較例１〜３で得られた発泡成形体は、着色むらが多く、外観が劣るものであった。
From the results shown in Table 1, Examples 1 to 4 using Solvent Blue 78 as a dye were beautifully colored, and high quality foamed molded articles with little coloring unevenness were obtained.
On the other hand, the foamed molded products obtained in Comparative Examples 1 to 3 using a dye different from Solvent Blue 78 had many uneven coloring 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、着色むらが無く、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を提供する。 The present invention relates to a foamable 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, easily producing a foamed molded product that is uniformly colored without uneven coloring. 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, and foam-molded products obtained by in-mold foam molding of the pre-foamed particles.
Claims (6)
前記染料がＳｏｌｖｅｎｔＢｌｕｅ７８を含有し、該染料とドデシルベンゼンスルホン酸ソーダとを水に予め分散させて投入し、かつスチレンを加えない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。 In a method for producing expandable polystyrene-based colored resin particles by placing polystyrene-based resin particles in a pressure-resistant container, and further adding a dye and a foaming agent to impregnate the polystyrene-based resin particles with the foaming agent and the dye,
A method for producing expandable polystyrene-based colored resin particles, wherein the dye contains Solvent Blue 78, the dye and sodium dodecylbenzenesulfonate are previously dispersed in water , and styrene is not added .
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